Mitochondrial Energy and Redox Signaling in Plants

Science.gov (United States)

Schwarzländer, Markus

2013-01-01

Abstract Significance: For a plant to grow and develop, energy and appropriate building blocks are a fundamental requirement. Mitochondrial respiration is a vital source for both. The delicate redox processes that make up respiration are affected by the plant's changing environment. Therefore, mitochondrial regulation is critically important to maintain cellular homeostasis. This involves sensing signals from changes in mitochondrial physiology, transducing this information, and mounting tailored responses, by either adjusting mitochondrial and cellular functions directly or reprogramming gene expression. Recent Advances: Retrograde (RTG) signaling, by which mitochondrial signals control nuclear gene expression, has been a field of very active research in recent years. Nevertheless, no mitochondrial RTG-signaling pathway is yet understood in plants. This review summarizes recent advances toward elucidating redox processes and other bioenergetic factors as a part of RTG signaling of plant mitochondria. Critical Issues: Novel insights into mitochondrial physiology and redox-regulation provide a framework of upstream signaling. On the other end, downstream responses to modified mitochondrial function have become available, including transcriptomic data and mitochondrial phenotypes, revealing processes in the plant that are under mitochondrial control. Future Directions: Drawing parallels to chloroplast signaling and mitochondrial signaling in animal systems allows to bridge gaps in the current understanding and to deduce promising directions for future research. It is proposed that targeted usage of new technical approaches, such as quantitative in vivo imaging, will provide novel leverage to the dissection of plant mitochondrial signaling. Antioxid. Redox Signal. 18, 2122–2144. PMID:23234467

Energy efficiency of neptunium redox battery in comparison with vanadium battery

International Nuclear Information System (INIS)

Yamamura, T.; Watanabe, N.; Shiokawa, Y.

2006-01-01

A neptunium ion possesses two isostructural and reversible redox couples (Np 3+ /Np 4+ and NpO 2 + /NpO 2 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 -2 , which exceeds that of the vanadium battery by ca. 16%

NAD(H) and NADP(H) Redox Couples and Cellular Energy Metabolism.

Science.gov (United States)

Xiao, Wusheng; Wang, Rui-Sheng; Handy, Diane E; Loscalzo, Joseph

2018-01-20

The nicotinamide adenine dinucleotide (NAD + )/reduced NAD + (NADH) and NADP + /reduced NADP + (NADPH) redox couples are essential for maintaining cellular redox homeostasis and for modulating numerous biological events, including cellular metabolism. Deficiency or imbalance of these two redox couples has been associated with many pathological disorders. Recent Advances: Newly identified biosynthetic enzymes and newly developed genetically encoded biosensors enable us to understand better how cells maintain compartmentalized NAD(H) and NADP(H) pools. The concept of redox stress (oxidative and reductive stress) reflected by changes in NAD(H)/NADP(H) has increasingly gained attention. The emerging roles of NAD + -consuming proteins in regulating cellular redox and metabolic homeostasis are active research topics. The biosynthesis and distribution of cellular NAD(H) and NADP(H) are highly compartmentalized. It is critical to understand how cells maintain the steady levels of these redox couple pools to ensure their normal functions and simultaneously avoid inducing redox stress. In addition, it is essential to understand how NAD(H)- and NADP(H)-utilizing enzymes interact with other signaling pathways, such as those regulated by hypoxia-inducible factor, to maintain cellular redox homeostasis and energy metabolism. Additional studies are needed to investigate the inter-relationships among compartmentalized NAD(H)/NADP(H) pools and how these two dinucleotide redox couples collaboratively regulate cellular redox states and cellular metabolism under normal and pathological conditions. Furthermore, recent studies suggest the utility of using pharmacological interventions or nutrient-based bioactive NAD + precursors as therapeutic interventions for metabolic diseases. Thus, a better understanding of the cellular functions of NAD(H) and NADP(H) may facilitate efforts to address a host of pathological disorders effectively. Antioxid. Redox Signal. 28, 251-272.

Calculating solution redox free energies with ab initio quantum mechanical/molecular mechanical minimum free energy path method

International Nuclear Information System (INIS)

Zeng Xiancheng; Hu Hao; Hu Xiangqian; Yang Weitao

2009-01-01

A quantum mechanical/molecular mechanical minimum free energy path (QM/MM-MFEP) method was developed to calculate the redox free energies of large systems in solution with greatly enhanced efficiency for conformation sampling. The QM/MM-MFEP method describes the thermodynamics of a system on the potential of mean force surface of the solute degrees of freedom. The molecular dynamics (MD) sampling is only carried out with the QM subsystem fixed. It thus avoids 'on-the-fly' QM calculations and thus overcomes the high computational cost in the direct QM/MM MD sampling. In the applications to two metal complexes in aqueous solution, the new QM/MM-MFEP method yielded redox free energies in good agreement with those calculated from the direct QM/MM MD method. Two larger biologically important redox molecules, lumichrome and riboflavin, were further investigated to demonstrate the efficiency of the method. The enhanced efficiency and uncompromised accuracy are especially significant for biochemical systems. The QM/MM-MFEP method thus provides an efficient approach to free energy simulation of complex electron transfer reactions.

The mechanism behind redox instability of anodes in high-temperature SOFCs

DEFF Research Database (Denmark)

Klemensø, Trine; Chung, Charissa; Larsen, Peter Halvor

2005-01-01

Bulk expansion of the anode upon oxidation is considered to be responsible for the lack of redox stability in high-temperature solid oxide fuel cells (SOFCs). The bulk expansion of nickel-yttria stabilized zirconia (YSZ) anode materials was measured by dilatometry as a function of sample geometry......, ceramic component, temperature, and temperature cycling. The strength of the ceramic network and the degree of Ni redistribution appeared to be key parameters of the redox behavior. A model of the redox mechanism in nickel-YSZ anodes was developed based on the dilatometry data and macro...

A high-energy-density redox flow battery based on zinc/polyhalide chemistry.

Science.gov (United States)

Zhang, Liqun; Lai, Qinzhi; Zhang, Jianlu; Zhang, Huamin

2012-05-01

Zn and the Art of Battery Development: A zinc/polyhalide redox flow battery employs Br(-) /ClBr(2-) and Zn/Zn(2+) redox couples in its positive and negative half-cells, respectively. The performance of the battery is evaluated by charge-discharge cycling tests and reveals a high energy efficiency of 81%, based on a Coulombic efficiency of 96% and voltage efficiency of 84%. The new battery technology can provide high performance and energy density at an acceptable cost. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient Solar Energy Harvesting and Storage through a Robust Photocatalyst Driving Reversible Redox Reactions.

Science.gov (United States)

Zhou, Yangen; Zhang, Shun; Ding, Yu; Zhang, Leyuan; Zhang, Changkun; Zhang, Xiaohong; Zhao, Yu; Yu, Guihua

2018-06-14

Simultaneous solar energy conversion and storage is receiving increasing interest for better utilization of the abundant yet intermittently available sunlight. Photoelectrodes driving nonspontaneous reversible redox reactions in solar-powered redox cells (SPRCs), which can deliver energy via the corresponding reverse reactions, present a cost-effective and promising approach for direct solar energy harvesting and storage. However, the lack of photoelectrodes having both high conversion efficiency and high durability becomes a bottleneck that hampers practical applications of SPRCs. Here, it is shown that a WO 3 -decorated BiVO 4 photoanode, without the need of extra electrocatalysts, can enable a single-photocatalyst-driven SPRC with a solar-to-output energy conversion efficiency as high as 1.25%. This SPRC presents stable performance over 20 solar energy storage/delivery cycles. The high efficiency and stability are attributed to the rapid redox reactions, the well-matched energy level, and the efficient light harvesting and charge separation of the prepared BiVO 4 . This demonstrated device system represents a potential alternative toward the development of low-cost, durable, and easy-to-implement solar energy technologies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Bulk energy storage increases United States electricity system emissions.

Science.gov (United States)

Hittinger, Eric S; Azevedo, Inês M L

2015-03-03

Bulk energy storage is generally considered an important contributor for the transition toward a more flexible and sustainable electricity system. Although economically valuable, storage is not fundamentally a "green" technology, leading to reductions in emissions. We model the economic and emissions effects of bulk energy storage providing an energy arbitrage service. We calculate the profits under two scenarios (perfect and imperfect information about future electricity prices), and estimate the effect of bulk storage on net emissions of CO2, SO2, and NOx for 20 eGRID subregions in the United States. We find that net system CO2 emissions resulting from storage operation are nontrivial when compared to the emissions from electricity generation, ranging from 104 to 407 kg/MWh of delivered energy depending on location, storage operation mode, and assumptions regarding carbon intensity. Net NOx emissions range from -0.16 (i.e., producing net savings) to 0.49 kg/MWh, and are generally small when compared to average generation-related emissions. Net SO2 emissions from storage operation range from -0.01 to 1.7 kg/MWh, depending on location and storage operation mode.

TEMPO-based catholyte for high-energy density nonaqueous redox flow batteries.

Science.gov (United States)

Wei, Xiaoliang; Xu, Wu; Vijayakumar, Murugesan; Cosimbescu, Lelia; Liu, Tianbiao; Sprenkle, Vincent; Wang, Wei

2014-12-03

A TEMPO-based non-aqueous electrolyte with the TEMPO concentration as high as 2.0 m is demonstrated as a high-energy-density catholyte for redox flow battery applications. With a hybrid anode, Li|TEMPO flow cells using this electrolyte deliver an energy efficiency of ca. 70% and an impressively high energy density of 126 W h L(-1) . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Sugar substitutes: their energy values, bulk characteristics, and potential health benefits.

Science.gov (United States)

Levin, G V; Zehner, L R; Saunders, J P; Beadle, J R

1995-11-01

Restriction of dietary energy extends life and reduces incidences of disease in animals. These benefits would likely extend to humans. However, diet restriction in animals imposes reductions of 30-50% in food intake, which is probably unacceptable to humans. Low-energy sweeteners used in beverages offer minor reductions in energy intake. However, they lack the bulk required for baked goods and other sugar-rich foods. Full-bulk sweeteners providing about one-half the energy of sugar are under development for such uses. Laxation limits their acceptable dose. Even within such limitations, they can help achieve the health benefits for humans indicated by diet restriction. D-Tagatose, a new candidate sweetener, is nearly as sweet as sucrose and has the bulk of sucrose, yet provides zero available energy. We discuss its potential contribution to human diet restriction along with its specific effect in delaying the aging effects of glycosylation.

2015 Progress Report/July 2016: Iron Oxide Redox Transformation Pathways: The Bulk Electrical Conduction Mechanism

Energy Technology Data Exchange (ETDEWEB)

Scherer, Michelle M. [Univ. of Iowa, Iowa City, IA (United States); Rosso, Kevin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2016-07-25

Despite decades of research on the reactivity and stable isotope properties of Fe oxides, the ability to describe the redox behavior of Fe oxides in the environment is still quite limited. This is due, in large part, to the analytical and spatial complexities associated with studying microscopic processes at the Fe oxide-water interface. This project had the long-term vision of filling this gap by developing a detailed understanding of the relationship between interfacial ET processes, surface structure and charge, and mineral semiconducting properties. We focused on the Fe(III)-oxides and oxyhydroxides because of their geochemical preponderance, versatility in synthesis of compositionally, structurally, and morphologically tailored phases, and because they are amenable to a wide range of surface and bulk properties characterization. In particular, reductive transformation of phases such as hematite (α-Fe₂O₃) and goethite (α-FeOOH) in aqueous solution can serve as excellent model systems for studies of electron conduction processes, as well as provide valuable insights into effect of nanoscale conductive materials on contaminant fate at DOE sites. More specifically, the goal of the Iowa component of this project was to use stable Fe isotope measurements to simultaneously measure isotope specific oxidation states and concentrations of Fe at the hematite-water and goethite-water interface. This work builds on our previous work where we used an innovative combination of ⁵⁷Fe Mössbauer spectroscopy and high precision isotope ratio measurements (MC-ICP-MS) to probe the dynamics of the reaction of aqueous Fe(II) with goethite. Mössbauer spectroscopy detects ⁵⁷Fe only among all other Fe isotopes and we have capitalized on this to spectroscopically demonstrate Fe(II)-Fe(III) electron transfer between sorbed Fe(II) and Fe(III) oxides (Handler, et al., 2009; Gorski, et al. 2010; Rosso et al., 2010). By combining the M�

A Membrane‐Free Redox Flow Battery with Two Immiscible Redox Electrolytes

OpenAIRE

Navalpotro, Paula; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

2017-01-01

Abstract Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short‐lifetimes, and expensive ion‐selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane‐free battery that relies on the immiscibility of redox electrolytes ...

Redox active polymers and colloidal particles for flow batteries

Science.gov (United States)

Gavvalapalli, Nagarjuna; Moore, Jeffrey S.; Rodriguez-Lopez, Joaquin; Cheng, Kevin; Shen, Mei; Lichtenstein, Timothy

2018-05-29

The invention provides a redox flow battery comprising a microporous or nanoporous size-exclusion membrane, wherein one cell of the battery contains a redox-active polymer dissolved in the non-aqueous solvent or a redox-active colloidal particle dispersed in the non-aqueous solvent. The redox flow battery provides enhanced ionic conductivity across the electrolyte separator and reduced redox-active species crossover, thereby improving the performance and enabling widespread utilization. Redox active poly(vinylbenzyl ethylviologen) (RAPs) and redox active colloidal particles (RACs) were prepared and were found to be highly effective redox species. Controlled potential bulk electrolysis indicates that 94-99% of the nominal charge on different RAPs is accessible and the electrolysis products are stable upon cycling. The high concentration attainable (>2.0 M) for RAPs in common non-aqueous battery solvents, their electrochemical and chemical reversibility, and their hindered transport across porous separators make them attractive materials for non-aqueous redox flow batteries based on size-selectivity.

Enhanced energy density of carbon-based supercapacitors using Cerium (III) sulphate as inorganic redox electrolyte

International Nuclear Information System (INIS)

Díaz, Patricia; González, Zoraida; Santamaría, Ricardo; Granda, Marcos; Menéndez, Rosa; Blanco, Clara

2015-01-01

Highlights: •Ce 2 (SO 4 ) 3 /H 2 SO 4 redox electrolyte as a new route to increase the energy density of SCs. •Increased operating cell voltage with no electrolyte decomposition. •Redox reactions on the battery-type electrode. •The negative electrode retains its capacitor behaviour. •Outstanding energy density values compared to those measured in H 2 SO 4 . -- ABSTRACT: The energy density of carbon based supercapacitors (CBSCs) was significantly increased by the addition of an inorganic redox species [Ce 2 (SO 4 ) 3 ] to an aqueous electrolyte (H 2 SO 4 ). The development of the faradaic processes on the positive electrode not only significantly increased the capacitance but also the operational cell voltage of these devices (up to 1.5 V) due to the high redox potentials at which the Ce 3+ /Ce 4+ reactions occur. Therefore, in asymmetric CBSCs assembled using an activated carbon as negative electrode and MWCNTs as the positive one, the addition of Ce 2 (SO 4 ) 3 moderately increases the energy density of the device (from 1.24 W h kg −1 to 5.08 W h kg −1 ). When a modified graphite felt is used as positive electrode the energy density of the cell reaches values as high as 13.84 W h kg −1 . The resultant systems become asymmetric hybrid devices where energy is stored due to the electrical double layer formation in the negative electrode and the development of the faradaic process in the positive electrode, which acts as a battery-type electrode

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.

Porphyrin-Based Symmetric Redox-Flow Batteries towards Cold-Climate Energy Storage.

Science.gov (United States)

Ma, Ting; Pan, Zeng; Miao, Licheng; Chen, Chengcheng; Han, Mo; Shang, Zhenfeng; Chen, Jun

2018-03-12

Electrochemical energy storage with redox-flow batteries (RFBs) under subzero temperature is of great significance for the use of renewable energy in cold regions. However, RFBs are generally used above 10 °C. Herein we present non-aqueous organic RFBs based on 5,10,15,20-tetraphenylporphyrin (H 2 TPP) as a bipolar redox-active material (anode: [H 2 TPP] 2- /H 2 TPP, cathode: H 2 TPP/[H 2 TPP] 2+ ) and a Y-zeolite-poly(vinylidene fluoride) (Y-PVDF) ion-selective membrane with high ionic conductivity as a separator. The constructed RFBs exhibit a high volumetric capacity of 8.72 Ah L -1 with a high voltage of 2.83 V and excellent cycling stability (capacity retention exceeding 99.98 % per cycle) in the temperature range between 20 and -40 °C. Our study highlights principles for the design of RFBs that operate at low temperatures, thus offering a promising approach to electrochemical energy storage under cold-climate conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy and Pitch Distribution of Spontaneously-generated High-energy Bulk Ions in the RFP

Science.gov (United States)

Kim, Jungha; Anderson, Jay; Reusch, Joshua; Eilerman, Scott; Capecchi, William

2014-10-01

Magnetic reconnection events in the reversed field pinch (RFP) are known to heat bulk and impurity ions. Runaway due to a parallel electric field has recently been confirmed as an important acceleration mechanism for high energy test ions supplied by a neutral beam. This effect does not, however, explain the change in distribution of nearly Maxwellian bulk ions at a reconnection event. By operating MST near maximum current and low electron density, significant fusion neutron flux can be generated without neutral beam injection. The bulk ion distribution created in these plasmas is well-confined, non-Maxwellian, and can be measured by the Advanced Neutral Particle Analyzer (ANPA) placed at a radial or tangential porthole. Data show a high energy tail up to 25 keV with a relatively higher signal in the low energy channels (8-15 keV) at the radial port following a reconnection event. Analysis of the energy dependence of trapped orbits sampled by the ANPA at the radial view implies an abundance of lower energy particles in regions of higher neutral density. This mandates a careful deconvolution of the measured ANPA signal to compute the fast ion distribution. This work is supported by the US DOE and NSF.

Singularities and Entropy in Bulk Viscosity Dark Energy Model

International Nuclear Information System (INIS)

Meng Xinhe; Dou Xu

2011-01-01

In this paper bulk viscosity is introduced to describe the effects of cosmic non-perfect fluid on the cosmos evolution and to build the unified dark energy (DE) with (dark) matter models. Also we derive a general relation between the bulk viscosity form and Hubble parameter that can provide a procedure for the viscosity DE model building. Especially, a redshift dependent viscosity parameter ζ ∝ λ 0 + λ 1 (1 + z) n proposed in the previous work [X.H. Meng and X. Dou, Commun. Theor. Phys. 52 (2009) 377] is investigated extensively in this present work. Further more we use the recently released supernova dataset (the Constitution dataset) to constrain the model parameters. In order to differentiate the proposed concrete dark energy models from the well known ΛCDM model, statefinder diagnostic method is applied to this bulk viscosity model, as a complementary to the Om parameter diagnostic and the deceleration parameter analysis performed by us before. The DE model evolution behavior and tendency are shown in the plane of the statefinder diagnostic parameter pair {r, s} as axes where the fixed point represents the ΛCDM model. The possible singularity property in this bulk viscosity cosmology is also discussed to which we can conclude that in the different parameter regions chosen properly, this concrete viscosity DE model can have various late evolution behaviors and the late time singularity could be avoided. We also calculate the cosmic entropy in the bulk viscosity dark energy frame, and find that the total entropy in the viscosity DE model increases monotonously with respect to the scale factor evolution, thus this monotonous increasing property can indicate an arrow of time in the universe evolution, though the quantum version of the arrow of time is still very puzzling. (geophysics, astronomy, and astrophysics)

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.

Probing the electronic structure of redox species and direct determination of intrinsic reorganization energies of electron transfer reactions

International Nuclear Information System (INIS)

Wang, Xue-Bin; Wang, Lai-Sheng

2000-01-01

An experimental technique capable of directly determining the intrinsic reorganization energies of bimolecular electron transfer reactions is described. Appropriate solution phase redox species are prepared in the gas phase using electrospray ionization and probed using photodetachment spectroscopy. Five metal complex anions involved in the Fe 2+ -Fe 3+ redox couple are investigated and the intramolecular reorganization energies are measured directly from spectral features due to removing the most loosely bound 3d electron from the Fe(II)-complexes. The photodetachment spectra also yield electronic structure information about the Fe 2+ -Fe 3+ redox couple and provide a common electronic structure origin for the reducing capability of the Fe(II)-complexes, the most common redox reagents. (c) 2000 American Institute of Physics

Enhancing Specific Energy and Power in Asymmetric Supercapacitors - A Synergetic Strategy based on the Use of Redox Additive Electrolytes

Science.gov (United States)

Singh, Arvinder; Chandra, Amreesh

2016-01-01

The strategy of using redox additive electrolyte in combination with multiwall carbon nanotubes/metal oxide composites leads to a substantial improvements in the specific energy and power of asymmetric supercapacitors (ASCs). When the pure electrolyte is optimally modified with a redox additive viz., KI, ~105% increase in the specific energy is obtained with good cyclic stability over 3,000 charge-discharge cycles and ~14.7% capacitance fade. This increase is a direct consequence of the iodine/iodide redox pairs that strongly modifies the faradaic and non-faradaic type reactions occurring on the surface of the electrodes. Contrary to what is shown in few earlier reports, it is established that indiscriminate increase in the concentration of redox additives will leads to performance loss. Suitable explanations are given based on theoretical laws. The specific energy or power values being reported in the fabricated ASCs are comparable or higher than those reported in ASCs based on toxic acetonitrile or expensive ionic liquids. The paper shows that the use of redox additive is economically favorable strategy for obtaining cost effective and environmentally friendly ASCs. PMID:27184260

Transfer of energy from irradiated crystals to redox reactions: iodide/bromate and nitrite/bromate systems

International Nuclear Information System (INIS)

Arnikar, H.J.; Madhava Rao, B.S.; Bedekar, M.J.

1978-01-01

Earlier it had been shown by the authors that some of the redox reactions, which do not take place at room temperature can be induced by γ radiation. The yields are proportional to the dose. Results reported here show that instead of direct irradiation, the energy stored in irradiated crystals in the form of F and hole centres can be available, in part, in effecting redox reactions. The mechanism of such an energy transfer is discussed with reference to reactions in the I - +BrO 3 - and NO 2 - +BrO 3 - systems due to the addition of irradiated NaCl. (author)

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...

A new class of solid oxide metal-air redox batteries for advanced stationary energy storage

Science.gov (United States)

Zhao, Xuan

Cost-effective and large-scale energy storage technologies are a key enabler of grid modernization. Among energy storage technologies currently being researched, developed and deployed, rechargeable batteries are unique and important that can offer a myriad of advantages over the conventional large scale siting- and geography- constrained pumped-hydro and compressed-air energy storage systems. However, current rechargeable batteries still need many breakthroughs in material optimization and system design to become commercially viable for stationary energy storage. This PhD research project investigates the energy storage characteristics of a new class of rechargeable solid oxide metal-air redox batteries (SOMARBs) that combines a regenerative solid oxide fuel cell (RSOFC) and hydrogen chemical-looping component. The RSOFC serves as the "electrical functioning unit", alternating between the fuel cell and electrolysis mode to realize discharge and charge cycles, respectively, while the hydrogen chemical-looping component functions as an energy storage unit (ESU), performing electrical-chemical energy conversion in situ via a H2/H2O-mediated metal/metal oxide redox reaction. One of the distinctive features of the new battery from conventional storage batteries is the ESU that is physically separated from the electrodes of RSOFC, allowing it to freely expand and contract without impacting the mechanical integrity of the entire battery structure. This feature also allows an easy switch in the chemistry of this battery. The materials selection for ESU is critical to energy capacity, round-trip efficiency and cost effectiveness of the new battery. Me-MeOx redox couples with favorable thermodynamics and kinetics are highly preferable. The preliminary theoretical analysis suggests that Fe-based redox couples can be a promising candidate for operating at both high and low temperatures. Therefore, the Fe-based redox-couple systems have been selected as the baseline for this

Characterization of a BODIPY Dye as an Active Species for Redox Flow Batteries.

Science.gov (United States)

Kosswattaarachchi, Anjula M; Friedman, Alan E; Cook, Timothy R

2016-12-08

An all-organic redox flow battery (RFB) employing a fluorescent boron-dipyrromethene (BODIPY) dye (PM567) was investigated. In a RFB, the stability of the electrolyte in all charged states is critically linked to coulombic efficiency. To evaluate stability, bulk electrolysis and cyclic voltammetry (CV) experiments were performed. Oxidized and reduced, PM567 does not remain intact; however, the products of bulk electrolysis evolve over time to show stable redox behavior, making the dye a precursor for the active species of an RFB. A theoretical cell potential of 2.32 V was predicted from CV experiments with a working discharge voltage of approximately 1.6 V in a static test cell. Mass spectrometry was used to identify the products of bulk electrolysis. Related experiments were carried out using ferrocene and cobaltocenium hexafluorophosphate as redox-stable benchmarks to further explain the stability results. The coulombic efficiency of a model cell using PM567 as a precursor for charge carriers stabilized around 73 %. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ruthenium based redox flow battery for solar energy storage

International Nuclear Information System (INIS)

Chakrabarti, Mohammed Harun; Roberts, Edward Pelham Lindfield; Bae, Chulheung; Saleem, Muhammad

2011-01-01

Research highlights: → Undivided redox flow battery employing porous graphite felt electrodes was used. → Ruthenium acetylacetonate dissolved in acetonitrile was the electrolyte. → Charge/discharge conditions were determined for both 0.02 M and 0.1 M electrolytes. → Optimum power output of 0.180 W was also determined for 0.1 M electrolyte. → 55% voltage efficiency was obtained when battery was full of electrolytes. -- Abstract: The technical performance for the operation of a stand alone redox flow battery system for solar energy storage is presented. An undivided reactor configuration has been employed along with porous graphite felt electrodes and ruthenium acetylacetonate as electrolyte in acetonitrile solvent. Limiting current densities are determined for concentrations of 0.02 M and 0.1 M ruthenium acetylacetonate. Based on these, operating conditions for 0.02 M ruthenium acetylacetonate are determined as charging current density of 7 mA/cm 2 , charge electrolyte superficial velocity of 0.0072 cm/s (through the porous electrodes), discharge current density of 2 mA/cm 2 and discharge electrolyte superficial velocity of 0.0045 cm/s. An optimum power output of 35 mW is also obtained upon discharge at 2.1 mA/cm 2 . With an increase in the concentration of ruthenium species from 0.02 M to 0.1 M, the current densities and power output are higher by a factor of five approximately (at same superficial velocities) due to higher mass transport phenomenon. Moreover at 0.02 M concentration the voltage efficiency is better for battery full of electrolytes prior to charging (52.1%) in comparison to an empty battery (40.5%) due to better mass transport phenomenon. Voltage efficiencies are higher as expected at concentrations of 0.1 M ruthenium acetylacetonate (55% when battery is full of electrolytes and 48% when empty) showing that the all-ruthenium redox flow battery has some promise for future applications in solar energy storage. Some improvements for the

Review of material research and development for vanadium redox flow battery applications

International Nuclear Information System (INIS)

Parasuraman, Aishwarya; Lim, Tuti Mariana; Menictas, Chris; Skyllas-Kazacos, Maria

2013-01-01

The vanadium redox flow battery (VRB) is one of the most promising electrochemical energy storage systems deemed suitable for a wide range of renewable energy applications that are emerging rapidly to reduce the carbon footprint of electricity generation. Though the Generation 1 Vanadium redox flow battery (G1 VRB) has been successfully implemented in a number of field trials and demonstration projects around the world, it suffers from low energy density that limits its use to stationary applications. Extensive research is thus being carried out to improve its energy density and enhance its performance to enable mobile applications while simultaneously trying to minimize the cost by employing cost effective stack materials and effectively controlling the current operating procedures. The vast bulk of this research was conducted at the University of New South Wales (UNSW) in Sydney during the period 1985–2005, with a large number of other research groups contributing to novel membrane and electrode material development since then. This paper presents a historical overview of materials research and development for the VRB at UNSW, highlighting some of the significant findings that have contributed to improving the battery's performance over the years. Relevant work in this field by other research groups in recent times has also been reviewed and discussed

On binding energy of trions in bulk materials

Science.gov (United States)

Filikhin, Igor; Kezerashvili, Roman Ya.; Vlahovic, Branislav

2018-03-01

We study the negatively T- and positively T+ charged trions in bulk materials in the effective mass approximation within the framework of a potential model. The binding energies of trions in various semiconductors are calculated by employing Faddeev equation in configuration space. Results of calculations of the binding energies for T- are consistent with previous computational studies and are in reasonable agreement with experimental measurements, while the T+ is unbound for all considered cases. The mechanism of formation of the binding energy of trions is analyzed by comparing contributions of a mass-polarization term related to kinetic energy operators and a term related to the Coulomb repulsion of identical particles.

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.

Membranes for Redox Flow Battery Applications

OpenAIRE

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

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...

Importance of the Reorganization Energy Barrier in Computational Design of Porphyrin-Based Solar Cells with Cobalt-Based Redox Mediators

DEFF Research Database (Denmark)

Ørnsø, Kristian Baruël; Jónsson, Elvar Örn; Jacobsen, Karsten Wedel

2015-01-01

, and this limits the achievable efficiency. Here we show that the large driving force is a direct consequence of the large reorganization energy of the dye regeneration reaction. The reorganization energies for charge transfer between a simple zinc porphyrin dye and two popular cobalt-based redox mediators......The shift from iodide-based redox mediators in dye-sensitized solar cells toward octahedral cobalt complexes has led to a significant increase in the efficiency. However, due to the nature of this type of complexes the driving force required for the regeneration of the dye is very high...... to identify already known highperformance dyes in addition to a number of even better candidates. Our analysis shows that the large internal reorganization energy of the Co-based redox mediators is an obstacle for achieving higher efficiencies....

Excitation energy of a helium 3 quasiparticle in the bulk mixture at constant pressure

International Nuclear Information System (INIS)

Yim, M.B.

1981-01-01

A 3 He quasiparticle excitation energy in bulk mixture at zero pressure and 6% solution is calculated to O(x) using the bulk effective interaction of Yim and Massey. The present 3 He quasiparticle excitation energy is in agreement with the experimental result of Hilton, Scherm and Stirling. (author)

Stand-alone wind system with Vanadium Redox Battery energy storage

DEFF Research Database (Denmark)

Teodorescu, Remus; Barote, L.; Weissbach, R.

2008-01-01

Energy storage devices are required for power balance and power quality in stand alone wind energy systems. A Vanadium Redox Flow Battery (VRB) system has many features which make its integration with a stand-alone wind energy system attractive. This paper proposes the integration of a VRB system...... with a typical stand-alone wind energy system during wind speed variation as well as transient performance under variable load. The investigated system consists of a variable speed wind turbine with permanent magnet synchronous generator (PMSG), diode rectifier bridge, buck-boost converter, bidirectional charge...... controller, transformer, inverter, ac loads and VRB (to store a surplus of wind energy and to supply power during a wind power shortage). The main purpose is to supply domestic appliances through a single phase 230V, 50Hz inverter. Simulations are accomplished in order to validate the stability of the supply....

Metal-Organic Frameworks as Highly Active Electrocatalysts for High-Energy Density, Aqueous Zinc-Polyiodide Redox Flow Batteries.

Science.gov (United States)

Li, Bin; Liu, Jian; Nie, Zimin; Wang, Wei; Reed, David; Liu, Jun; McGrail, Pete; Sprenkle, Vincent

2016-07-13

The new aqueous zinc-polyiodide redox flow battery (RFB) system with highly soluble active materials as well as ambipolar and bifunctional designs demonstrated significantly enhanced energy density, which shows great potential to reduce RFB cost. However, the poor kinetic reversibility and electrochemical activity of the redox reaction of I3(-)/I(-) couples on graphite felts (GFs) electrode can result in low energy efficiency. Two nanoporous metal-organic frameworks (MOFs), MIL-125-NH2 and UiO-66-CH3, that have high surface areas when introduced to GF surfaces accelerated the I3(-)/I(-) redox reaction. The flow cell with MOF-modified GFs serving as a positive electrode showed higher energy efficiency than the pristine GFs; increases of about 6.4% and 2.7% occurred at the current density of 30 mA/cm(2) for MIL-125-NH2 and UiO-66-CH3, respectively. Moreover, UiO-66-CH3 is more promising due to its excellent chemical stability in the weakly acidic electrolyte. This letter highlights a way for MOFs to be used in the field of RFBs.

Redox dependent behaviour of molybdenum during magmatic processes in the terrestrial and lunar mantle: Implications for the Mo/W of the bulk silicate Moon

Science.gov (United States)

Leitzke, F. P.; Fonseca, R. O. C.; Sprung, P.; Mallmann, G.; Lagos, M.; Michely, L. T.; Münker, C.

2017-09-01

We present results of high-temperature olivine-melt, pyroxene-melt and plagioclase-melt partitioning experiments aimed at investigating the redox transition of Mo in silicate systems. Data for a series of other minor and trace elements (Sc, Ba, Sr, Cr, REE, Y, HFSE, U, Th and W) were also acquired to constrain the incorporation of Mo in silicate minerals. All experiments were carried out in vertical tube furnaces at 1 bar and temperatures ranging from ca. 1220 to 1300 °C. Oxygen fugacity was controlled via CO-CO2 gas mixtures and varied systematically from 5.5 log units below to 1.9 log units above the fayalite-magnetite-quartz (FMQ) redox buffer thereby covering the range in oxygen fugacities of terrestrial and lunar basalt genesis. Molybdenum is shown to be volatile at oxygen fugacities above FMQ and that its compatibility in pyroxene and olivine increases three orders of magnitude towards the more reducing conditions covered in this study. The partitioning results show that Mo is dominantly tetravalent at redox conditions below FMQ-4 and dominantly hexavalent at redox conditions above FMQ. Given the differences in oxidation states of the terrestrial (oxidized) and lunar (reduced) mantles, molybdenum will behave significantly differently during basalt genesis in the Earth (i.e. highly incompatible; average DMoperidotite/melt ∼ 0.008) and Moon (i.e. moderately incompatible/compatible; average DMoperidotite/melt ∼ 0.6). Thus, it is expected that Mo will strongly fractionate from W during partial melting in the lunar mantle, given that W is broadly incompatible at FMQ-5. Moreover, the depletion of Mo and the Mo/W range in lunar samples can be reproduced by simply assuming a primitive Earth-like Mo/W for the bulk silicate Moon. Such a lunar composition is in striking agreement with the Moon being derived from the primitive terrestrial mantle after core formation on Earth.

Influence of increment thickness on radiant energy and microhardness of bulk-fill resin composites.

Science.gov (United States)

Karacolak, Gamze; Turkun, L Sebnem; Boyacioglu, Hayal; Ferracane, Jack L

2018-03-30

Determining the energy transferred at the bottom of eleven bulk-fill resin composites, comparing top and bottom microhardness's and evaluating the correlation between microhardness and radiant energy were aimed. Samples were placed over the bottom sensor of a visible light transmission spectrophotometer and polymerized for 20 s. The bottom and top Knoop microhardness were measured. Paired t-test and correlation analysis were used for statistics (p≤0.05). In all groups, the bottom radiant energy decreased significantly with increasing thickness. For groups of Aura 2 mm, X-tra Fil 2 and 4 mm, SDR 2 and 4 mm, X-tra Base 2 mm no significant difference was found between top and bottom microhardness. For the bottom levels of Aura, X-tra Fil, Filtek Bulk-Fill Posterior, SDR, X-tra Base groups no significant difference was found between the microhardness's of 2 and 4 mm thicknesses. For X-tra Fil, Tetric Evo Ceram Bulk-Fill, Filtek Bulk-Fill Flowable and Z100 groups radiant energy affected positively the microhardness.

Redox electrode materials for supercapatteries

OpenAIRE

Yu, Linpo; Chen, George Z.

2016-01-01

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...

Considering a Threshold Energy in Reactive Transport Modeling of Microbially Mediated Redox Reactions in an Arsenic-Affected Aquifer

Directory of Open Access Journals (Sweden)

Marco Rotiroti

2018-01-01

Full Text Available The reductive dissolution of Fe-oxide driven by organic matter oxidation is the primary mechanism accepted for As mobilization in several alluvial aquifers. These processes are often mediated by microorganisms that require a minimum Gibbs energy available to conduct the reaction in order to sustain their life functions. Implementing this threshold energy in reactive transport modeling is rarely used in the existing literature. This work presents a 1D reactive transport modeling of As mobilization by the reductive dissolution of Fe-oxide and subsequent immobilization by co-precipitation in iron sulfides considering a threshold energy for the following terminal electron accepting processes: (a Fe-oxide reduction, (b sulfate reduction, and (c methanogenesis. The model is then extended by implementing a threshold energy on both reaction directions for the redox reaction pairs Fe(III reduction/Fe(II oxidation and methanogenesis/methane oxidation. The optimal threshold energy fitted in 4.50, 3.76, and 1.60 kJ/mol e− for sulfate reduction, Fe(III reduction/Fe(II oxidation, and methanogenesis/methane oxidation, respectively. The use of models implementing bidirectional threshold energy is needed when a redox reaction pair can be transported between domains with different redox potentials. This may often occur in 2D or 3D simulations.

7D Randall-Sundrum cosmology, brane-bulk energy exchange, and holography

International Nuclear Information System (INIS)

Mazzanti, Liuba

2008-01-01

We discuss the cosmological implications and the holographic dual theory of the 7D Randall-Sundrum gravitational setup. Adding generic matter in the bulk on the 7D gravity side, we study the cosmological evolution inferred by the nonvanishing value of the brane-bulk energy exchange parameter. This analysis is achieved in detail for specific assumptions on the internal space evolution, including analytical considerations and numerical results. The dual theory is then constructed, making use of the holographic renormalization procedure. The resulting renormalized 6D conformal field theory is anomalous and coupled to 6D gravity plus higher order corrections. The critical point analysis on the brane is performed. Finally, we sketch a comparison between the two dual descriptions. We moreover generalize the Ads/CFT dual theory to the nonconformal and interacting case, relating the energy exchange parameter of the bulk gravity description to the new interactions between hidden and visible sectors.

Redox Homeostasis in Plants under Abiotic Stress: Role of electron carriers, energy metabolism mediators and proteinaceous thiols

Directory of Open Access Journals (Sweden)

Dhriti Kapoor

2015-03-01

Full Text Available Contemporaneous presence of both oxidized and reduced forms of electron carriers is mandatory in efficient flux by plant electron transport cascades. This requirement is considered as redox poising that involves the movement of electron from multiple sites in respiratory and photosynthetic electron transport chains to molecular oxygen. This flux triggers the formation of superoxide, consequently give rise to other reactive oxygen species (ROS under adverse environmental conditions like drought, high or low temperature, heavy metal stress etc. that plants owing during their life span. Plant cells synthesize ascorbate, an additional hydrophilic redox buffer, which protect the plants against oxidative challenge. Large pools of antioxidants also preside over the redox homeostasis. Besides, tocopherol is a liposoluble redox buffer, which efficiently scavenges the ROS like singlet oxygen. In addition, proteinaceous thiol members such as thioredoxin, peroxiredoxin and glutaredoxin, electron carriers and energy metabolism mediators phosphorylated (NADP and non-phosphorylated (NAD+ coenzyme forms interact with ROS, metabolize and maintain redox homeostasis.

Redox properties of structural Fe in clay minerals: 3. Relationships between smectite redox and structural properties.

Science.gov (United States)

Gorski, Christopher A; Klüpfel, Laura E; Voegelin, Andreas; Sander, Michael; Hofstetter, Thomas B

2013-01-01

Structural Fe in clay minerals is an important redox-active species in many pristine and contaminated environments as well as in engineered systems. Understanding the extent and kinetics of redox reactions involving Fe-bearing clay minerals has been challenging due to the inability to relate structural Fe(2+)/Fe(total) fractions to fundamental redox properties, such as reduction potentials (EH). Here, we overcame this challenge by using mediated electrochemical reduction (MER) and oxidation (MEO) to characterize the fraction of redox-active structural Fe (Fe(2+)/Fe(total)) in smectites over a wide range of applied EH-values (-0.6 V to +0.6 V). We examined Fe(2+)/Fe(total )- EH relationships of four natural Fe-bearing smectites (SWy-2, SWa-1, NAu-1, NAu-2) in their native, reduced, and reoxidized states and compared our measurements with spectroscopic observations and a suite of mineralogical properties. All smectites exhibited unique Fe(2+)/Fe(total) - EH relationships, were redox active over wide EH ranges, and underwent irreversible electron transfer induced structural changes that were observable with X-ray absorption spectroscopy. Variations among the smectite Fe(2+)/Fe(total) - EH relationships correlated well with both bulk and molecular-scale properties, including Fe(total) content, layer charge, and quadrupole splitting values, suggesting that multiple structural parameters determined the redox properties of smectites. The Fe(2+)/Fe(total) - EH relationships developed for these four commonly studied clay minerals may be applied to future studies interested in relating the extent of structural Fe reduction or oxidation to EH-values.

Enhanced reversibility and durability of a solid oxide Fe-air redox battery by carbothermic reaction derived energy storage materials.

Science.gov (United States)

Zhao, Xuan; Li, Xue; Gong, Yunhui; Huang, Kevin

2014-01-18

The recently developed solid oxide metal-air redox battery is a new technology capable of high-rate chemistry. Here we report that the performance, reversibility and stability of a solid oxide iron-air redox battery can be significantly improved by nanostructuring energy storage materials from a carbothermic reaction.

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.

New lab scale approaches for quantification of redox conditions

Science.gov (United States)

Fernandez, P. M.; Dathe, A.; Nadeem, S.; Bakken, L. R.; Bloem, E.; French, H. K.; Binley, A. M.

2013-12-01

Degradation of organic chemicals in the unsaturated zone is a process highly relevant for developing remediation techniques for protecting groundwater. Degradation causes changes in chemical composition of the water phase and gas releases. These changes can potentially be mapped with electrical resistivity measurements in the bulk soil and gas measurements at the soil surface. The redox potential combined with the local geological conditions determines the composition of available electron acceptors as well as microbial degradation pathways and how the soil system is affected in the long term. After oxygen and nitrate are depleted, manganese and iron should be reduced. However, in experiments conducted in the unsaturated zone at Gardermoen airport, Norway, it was found that for the degradation of the de-icing agent propylene glycol (PG), manganese and iron were preferred over nitrate as electron acceptor. A key hypothesis for the work presented is that for a designated soil, the redox potential affects gas releases and soil solution composition profoundly. As the redox potential decreases, the reactants of the degradation change and therefore the composition of the soil-water system changes. These changes can be quantified dynamically by gas measurements and changes in electrical conductivity of the pore water and electrical resistivity of the bulk soil. Batch experiments were conducted to examine whether nitrate is a preferred electron acceptor over iron and manganese oxides as described in classical redox reaction theory. Gas releases during PG and glutamate degradation were measured in a sandy pristine soil with and without nitrate under anaerobic condition during two weeks of incubation. Chemical reactions were quantified with the modelling tool ORCHESTRA. We are currently investigating whether dynamical measurements of electrical conductivity and bulk resistivity are suited to trace which electron acceptors (nitrate, manganese or iron) are being reduced. First

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.

TiO2-photoanode-assisted direct solar energy harvesting and storage in a solar-powered redox cell using halides as active materials.

Science.gov (United States)

Zhang, Shun; Chen, Chen; Zhou, Yangen; Qian, Yumin; Ye, Jing; Xiong, Shiyun; Zhao, Yu; Zhang, Xiaohong

2018-06-19

The rapid deployment of renewable energy is resulting in significant energy security, climate change mitigation, and economic benefits. We demonstrate here the direct solar energy harvesting and storage in a rechargeable solar-powered redox cell, which can be charged solely by solar irradiation. The cell follows a conventional redox-flow cell design with one integrated TiO2 photoanode in the cathode side. Direct charging the cell by solar irradiation results in the conversion of solar energy in to chemical energy. While discharging the cell leads to the release of chemical energy in the form of electricity. The cell integrates energy conversion and storage processes in a single device, making the solar energy directly and efficiently dispatchable. When using redox couples of Br2/Br- and I3-/I- in the cathode side and anode side, respectively, the cell can be directly charged upon solar irradiation, yielding a discharge potential of 0.5V with good round-trip efficiencies. This design is expected to be a potential alternative towards the development of affordable, inexhaustible and clean solar energy technologies.

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent Effect on Redox Properties of Hexanethiolate Monolayer-Protected Gold Nanoclusters

OpenAIRE

Su, B; Zhang, M; Shao, Y; Girault, HH

2006-01-01

The capacitance of monolayer-protected gold nanoclusters (MPCs), CMPC, in solution has been theoretically reconsidered from an electrostatic viewpoint, in which an MPC is considered as an isolated charged sphere within two dielectric layers, the intrinsic coating monolayer, and the bulk solvent. The model predicts that the bulk solvent provides an important contribution to CMPC and influences the redox properties of MPCs. This theoretical prediction is then examined experimentally by comparin...

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

Science.gov (United States)

Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

2015-06-11

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

Mitochondrial redox biology and homeostasis in plants.

Science.gov (United States)

Noctor, Graham; De Paepe, Rosine; Foyer, Christine H

2007-03-01

Mitochondria are key players in plant cell redox homeostasis and signalling. Earlier concepts that regarded mitochondria as secondary to chloroplasts as the powerhouses of photosynthetic cells, with roles in cell proliferation, death and ageing described largely by analogy to animal paradigms, have been replaced by the new philosophy of integrated cellular energy and redox metabolism involving mitochondria and chloroplasts. Thanks to oxygenic photosynthesis, plant mitochondria often operate in an oxygen- and carbohydrate-rich environment. This rather unique environment necessitates extensive flexibility in electron transport pathways and associated NAD(P)-linked enzymes. In this review, mitochondrial redox metabolism is discussed in relation to the integrated cellular energy and redox function that controls plant cell biology and fate.

Revisiting the BaO2/BaO redox cycle for solar thermochemical energy storage.

Science.gov (United States)

Carrillo, A J; Sastre, D; Serrano, D P; Pizarro, P; Coronado, J M

2016-03-21

The barium peroxide-based redox cycle was proposed in the late 1970s as a thermochemical energy storage system. Since then, very little attention has been paid to such redox couples. In this paper, we have revisited the use of reduction-oxidation reactions of the BaO2/BaO system for thermochemical heat storage at high temperatures. Using thermogravimetric analysis, reduction and oxidation reactions were studied in order to find the main limitations associated with each process. Furthermore, the system was evaluated through several charge-discharge stages in order to analyse its possible degradation after repeated cycling. Through differential scanning calorimetry the heat stored and released were also determined. Oxidation reaction, which was found to be slower than reduction, was studied in more detail using isothermal tests. It was observed that the rate-controlling step of BaO oxidation follows zero-order kinetics, although at high temperatures a deviation from Arrhenius behaviour was observed probably due to hindrances to anionic oxygen diffusion caused by the formation of an external layer of BaO2. This redox couple was able to withstand several redox cycles without deactivation, showing reaction conversions close to 100% provided that impurities are previously eliminated through thermal pre-treatment, demonstrating the feasibility of this system for solar thermochemical heat storage.

Membranes for Redox Flow Battery Applications

Science.gov (United States)

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

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. 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. PMID:24958177

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.

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.

Spectroscopic evidence of resonance energy transfer mechanism from PbS QDs to bulk silicon

Directory of Open Access Journals (Sweden)

Bernechea M.

2013-06-01

Full Text Available In this work, we study the efficiency of the resonance energy transfer from PbS quantum dots to bulk silicon. We present spectroscopic evidence that resonance energy transfer from PbS quantum dots to bulk silicon can be an efficient process for separation distances below 12 nm. Temperature measurements are also presented for PbS quantum dots deposited on glass and silicon with 5 nm and 20nm spacer thicknesses substrates. Our findings show that the resonance energy transfer efficiency remains constant over the 50K to 300K temperature range.

High-energy-density, aqueous, metal-polyiodide redox flow batteries

Science.gov (United States)

Li, Bin; Nie, Zimin; Wang, Wei; Liu, Jun; Sprenkle, Vincent L.

2017-08-29

Improved metal-based redox flow batteries (RFBs) can utilize a metal and a divalent cation of the metal (M.sup.2+) as an active redox couple for a first electrode and electrolyte, respectively, in a first half-cell. For example, the metal can be Zn. The RFBs can also utilize a second electrolyte having I.sup.-, anions of I.sub.x (for x.gtoreq.3), or both in an aqueous solution, wherein the I.sup.- and the anions of I.sub.x (for x.gtoreq.3) compose an active redox couple in a second half-cell.

Redox-flow battery of actinide complexes

International Nuclear Information System (INIS)

Yamamura, Tomoo; Shiokawa, Yoshinobu

2006-01-01

Np battery and U battery were developed. We suggested that Np redox-flow battery should be (-)|Np 3+ ,Np 4+ ||NpO 2 + ,NpO 2 2+ |(+), and U battery (-)|[U III T 2 ] - ,[U IV T 2 ] 0 ||[U V O 2 T] - ,[U VI O 2 T] 0 |(+). The electromotive force at 50 % charge of Np and U battery is 1.10 V and 1.04 V, respectively. The energy efficiency of 70 mA/cm 2 of Np and U battery shows 99 % and 98 %, respectively. V redox-flow battery, electrode reactions of An battery, Np battery, U battery and future of U battery are described. The concept of V redox-flow battery, comparison of energy efficiency of Np, U and V battery, oxidation state and ionic species of 3d transition metals and main An, Purbe diagram of Np and U aqueous solution, shift of redox potential of β-diketones by pKa, and specifications of three redox-flow batteries are reported. (S.Y.)

A Membrane‐Free Redox Flow Battery with Two Immiscible Redox Electrolytes

Science.gov (United States)

Navalpotro, Paula; Palma, Jesus; Anderson, Marc

2017-01-01

Abstract Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short‐lifetimes, and expensive ion‐selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane‐free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof‐of‐concept of a membrane‐free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L−1, and is able to deliver 90 % of its theoretical capacity while showing excellent long‐term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). PMID:28658538

A Membrane-Free Redox Flow Battery with Two Immiscible Redox Electrolytes.

Science.gov (United States)

Navalpotro, Paula; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

2017-10-02

Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short-lifetimes, and expensive ion-selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane-free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof-of-concept of a membrane-free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L -1 , and is able to deliver 90 % of its theoretical capacity while showing excellent long-term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Entropy production and energy dissipation in symmetric redox supercapacitors

Science.gov (United States)

Palma-Aramburu, N.; Santamaría-Holek, I.

2017-08-01

In this work we propose a theoretical model that accounts for the main features of the loading-unloading process of a symmetric redox MnO2-based supercapacitor dominated by fast electrochemical reactions at the electrodes. The model is formulated on the basis of nonequilibrium thermodynamics from which we are able to deduce generalized expressions for the electrochemical affinity, the load-voltage and the current-voltage equations that constitute generalizations of the current-overpotential and Butler-Volmer equations, and that are used to describe experimental voltagram data with good agreement. These equations allowed us to derive the behavior of the energy dissipated per cycle showing that it has a nonmonotonic behavior and that in the operation regime it follows a power-law behavior as a function of the frequency. The existence of a maximum for the energy dissipated as a function of the frequency suggests the that the corresponding optimal operation frequency should be similar in value to ωmax.

A high energy microscope for local strain measurements within bulk materials

DEFF Research Database (Denmark)

Lienert, U.; Poulsen, H.F.; Martins, R.V.

2000-01-01

A novel diffraction technique for local, three dimensional strain scanning within bulk materials is presented. The technique utilizes high energy, micro-focussed synchrotron radiation which can penetrate several millimeters into typical metals. The spatial resolution can be as narrow as 1 mum...... in one dimension and in three dimensions about 5x10x100 mum(3) Bulk properties are probed non-destructively and in-situ measurements during thermo-mechanical processing are feasible. A dedicated experimental station has been constructed at the ID11 beamline of the European Synchrotron Radiation Facility...

Opportunities for shear energy scaling in bulk acoustic wave resonators

NARCIS (Netherlands)

Jose, Sumy; Hueting, Raymond Josephus Engelbart

2014-01-01

An important energy loss contribution in bulk acoustic wave resonators is formed by so-called shear waves, which are transversal waves that propagate vertically through the devices with a horizontal motion. In this work, we report for the first time scaling of the shear-confined spots, i.e., spots

High Performance Hydrogen/Bromine Redox Flow Battery for Grid-Scale Energy Storage

Energy Technology Data Exchange (ETDEWEB)

Cho, KT; Ridgway, P; Weber, AZ; Haussener, S; Battaglia, V; Srinivasan, V

2012-01-01

The electrochemical behavior of a promising hydrogen/bromine redox flow battery is investigated for grid-scale energy-storage application with some of the best redox-flow-battery performance results to date, including a peak power of 1.4 W/cm(2) and a 91% voltaic efficiency at 0.4 W/cm(2) constant-power operation. The kinetics of bromine on various materials is discussed, with both rotating-disk-electrode and cell studies demonstrating that a carbon porous electrode for the bromine reaction can conduct platinum-comparable performance as long as sufficient surface area is realized. The effect of flow-cell designs and operating temperature is examined, and ohmic and mass-transfer losses are decreased by utilizing a flow-through electrode design and increasing cell temperature. Charge/discharge and discharge-rate tests also reveal that this system has highly reversible behavior and good rate capability. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.018211jes] All rights reserved.

Non-minimal derivative coupling scalar field and bulk viscous dark energy

Energy Technology Data Exchange (ETDEWEB)

Mostaghel, Behrang [Shahid Beheshti University, Department of Physics, Tehran (Iran, Islamic Republic of); Moshafi, Hossein [Institute for Advanced Studies in Basic Sciences, Department of Physics, Zanjan (Iran, Islamic Republic of); Movahed, S.M.S. [Shahid Beheshti University, Department of Physics, Tehran (Iran, Islamic Republic of); Institute for Research in Fundamental Sciences (IPM), School of Physics, Tehran (Iran, Islamic Republic of)

2017-08-15

Inspired by thermodynamical dissipative phenomena, we consider bulk viscosity for dark fluid in a spatially flat two-component Universe. Our viscous dark energy model represents phantom-crossing which avoids big-rip singularity. We propose a non-minimal derivative coupling scalar field with zero potential leading to accelerated expansion of the Universe in the framework of bulk viscous dark energy model. In this approach, the coupling constant, κ, is related to viscosity coefficient, γ, and the present dark energy density, Ω{sub DE}{sup 0}. This coupling is bounded as κ element of [-1/9H{sub 0}{sup 2}(1 - Ω{sub DE}{sup 0}), 0]. We implement recent observational data sets including a joint light-curve analysis (JLA) for SNIa, gamma ray bursts (GRBs) for most luminous astrophysical objects at high redshifts, baryon acoustic oscillations (BAO) from different surveys, Hubble parameter from HST project, Planck CMB power spectrum and lensing to constrain model free parameters. The joint analysis of JLA + GRBs + BAO + HST shows that Ω{sub DE}{sup 0} = 0.696 ± 0.010, γ = 0.1404 ± 0.0014 and H{sub 0} = 68.1 ± 1.3. Planck TT observation provides γ = 0.32{sup +0.31}{sub -0.26} in the 68% confidence limit for the viscosity coefficient. The cosmographic distance ratio indicates that current observed data prefer to increase bulk viscosity. The competition between phantom and quintessence behavior of the viscous dark energy model can accommodate cosmological old objects reported as a sign of age crisis in the ΛCDM model. Finally, tension in the Hubble parameter is alleviated in this model. (orig.)

Model for Calculating Electrolytic Shunt Path Losses in Large Electrochemical Energy Conversion Systems

Science.gov (United States)

Prokopius, P. R.

1976-01-01

Generalized analysis and solution techniques were developed to evaluate the shunt power losses in electrochemical systems designed with a common or circulating electrolyte supply. Sample data are presented for a hypothetical bulk energy storage redox system, and the general applicability of the analysis technique is discussed.

Bulk Materials Analysis Using High-Energy Positron Beams

International Nuclear Information System (INIS)

Glade, S C; Asoka-Kumar, P; Nieh, T G; Sterne, P A; Wirth, B D; Dauskardt, R H; Flores, K M; Suh, D; Odette, G.R.

2002-01-01

This article reviews some recent materials analysis results using high-energy positron beams at Lawrence Livermore National Laboratory. We are combining positron lifetime and orbital electron momentum spectroscopic methods to provide electron number densities and electron momentum distributions around positron annihilation sites. Topics covered include: correlation of positron annihilation characteristics with structural and mechanical properties of bulk metallic glasses, compositional studies of embrittling features in nuclear reactor pressure vessel steel, pore characterization in Zeolites, and positron annihilation characteristics in alkali halides

Design rules for donors in bulk-heterojunction solar cells - towards 10 % energy-conversion efficiency

Energy Technology Data Exchange (ETDEWEB)

Scharber, M.C.; Muehlbacher, D.; Koppe, M.; Denk, P.; Waldauf, C.; Brabec, C.J. [Konarka Austria, Altenbergerstrasse 69, A-4040 Linz (Austria); Heeger, A.J. [Department of Materials Science, Broida Hall 6125, University of California at Santa Barbara, Santa Barbara, CA 3106-5090 (United States)

2006-03-17

For bulk-heterojunction photovoltaic cells fabricated from conjugated polymers and a fullerene derivative, the relation between the open-circuit voltage (V{sub oc}) and the oxidation potential for different conjugated polymers is studied. A linear relation between V{sub oc} and the oxidation potential is found (see figure). Based on this relation, the energy-conversion efficiency of a bulk-heterojunction solar cell is derived as a function of the bandgap and the energy levels of the conjugated polymer. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

Large temporal scale and capacity subsurface bulk energy storage with CO2

Science.gov (United States)

Saar, M. O.; Fleming, M. R.; Adams, B. M.; Ogland-Hand, J.; Nelson, E. S.; Randolph, J.; Sioshansi, R.; Kuehn, T. H.; Buscheck, T. A.; Bielicki, J. M.

2017-12-01

Decarbonizing energy systems by increasing the penetration of variable renewable energy (VRE) technologies requires efficient and short- to long-term energy storage. Very large amounts of energy can be stored in the subsurface as heat and/or pressure energy in order to provide both short- and long-term (seasonal) storage, depending on the implementation. This energy storage approach can be quite efficient, especially where geothermal energy is naturally added to the system. Here, we present subsurface heat and/or pressure energy storage with supercritical carbon dioxide (CO2) and discuss the system's efficiency, deployment options, as well as its advantages and disadvantages, compared to several other energy storage options. CO2-based subsurface bulk energy storage has the potential to be particularly efficient and large-scale, both temporally (i.e., seasonal) and spatially. The latter refers to the amount of energy that can be stored underground, using CO2, at a geologically conducive location, potentially enabling storing excess power from a substantial portion of the power grid. The implication is that it would be possible to employ centralized energy storage for (a substantial part of) the power grid, where the geology enables CO2-based bulk subsurface energy storage, whereas the VRE technologies (solar, wind) are located on that same power grid, where (solar, wind) conditions are ideal. However, this may require reinforcing the power grid's transmission lines in certain parts of the grid to enable high-load power transmission from/to a few locations.

Bulk single crystal ternary substrates for a thermophotovoltaic energy conversion system

Science.gov (United States)

Charache, Greg W.; Baldasaro, Paul F.; Nichols, Greg J.

1998-01-01

A thermophotovoltaic energy conversion device and a method for making the device. The device includes a substrate formed from a bulk single crystal material having a bandgap (E.sub.g) of 0.4 eVternary or quaternary III-V semiconductor active layers.

Morphology evolution and nanostructure of chemical looping transition metal oxide materials upon redox processes

International Nuclear Information System (INIS)

Qin, Lang; Cheng, Zhuo; Guo, Mengqing; Fan, Jonathan A.; Fan, Liang-Shih

2017-01-01

Transition metal are heavily used in chemical looping technologies because of their high oxygen carrying capacity and high thermal reactivity. These oxygen activities result in the oxide formation and oxygen vacancy formation that affect the nanoscale crystal phase and morphology within these materials and their subsequent bulk chemical behavior. In this study, two selected earlier transition metals manganese and cobalt as well as two selected later transition metals copper and nickel that are important to chemical looping reactions are investigated when they undergo cyclic redox reactions. We found Co microparticles exhibited increased CoO impurity presence when oxidized to Co_3O_4 upon cyclic oxidation; CuO redox cycles prefer to be limited to a reduced form of Cu_2O and an oxidized form of CuO; Mn microparticles were oxidized to a mixed phases of MnO and Mn_3O_4, which causes delamination during oxidation. For Ni microparticles, a dense surface were observed during the redox reaction. The atomistic thermodynamics methods and density functional theory (DFT) calculations are carried out to elucidate the effect of oxygen dissociation and migration on the morphological evolution of nanostructures during the redox processes. Our results indicate that the earlier transition metals (Mn and Co) tend to have stronger interaction with O_2 than the later transition metals (Ni and Cu). Also, our modified Brønsted−Evans−Polanyi (BEP) relationship for reaction energies and total reaction barriers reveals that reactions of earlier transition metals are more exergonic and have lower oxygen dissociation barriers than those of later transition metals. In addition, it was found that for these transition metal oxides the oxygen vacancy formation energies increase with the depth. The oxide in the higher oxidation state of transition metal has lower vacancy formation energy, which can facilitate forming the defective nanostructures. The fundamental understanding of these metal

STAT3-RXR-Nrf2 activates systemic redox and energy homeostasis upon steep decline in pO2 gradient

Directory of Open Access Journals (Sweden)

Subhojit Paul

2018-04-01

Full Text Available Hypobaric hypoxia elicits several patho-physiological manifestations, some of which are known to be lethal. Among various molecular mechanisms proposed so far, perturbation in redox state due to imbalance between radical generation and antioxidant defence is promising. These molecular events are also related to hypoxic status of cancer cells and therefore its understanding has extended clinical advantage beyond high altitude hypoxia. In present study, however, the focus was to understand and propose a model for rapid acclimatization of high altitude visitors to enhance their performance based on molecular changes. We considered using simulated hypobaric hypoxia at some established thresholds of high altitude stratification based on known physiological effects. Previous studies have focused on the temporal aspect while overlooking the effects of varying pO2 levels during exposure to hypobaric hypoxia. The pO2 levels, indicative of altitude, are crucial to redox homeostasis and can be the limiting factor during acclimatization to hypobaric hypoxia. In this study we present the effects of acute (24 h exposure to high (3049 m; pO2: 71 kPa, very high (4573 m; pO2: 59 kPa and extreme altitude (7620 m; pO2: 40 kPa zones on lung and plasma using semi-quantitative redox specific transcripts and quantitative proteo-bioinformatics workflow in conjunction with redox stress assays. It was observed that direct exposure to extreme altitude caused 100% mortality, which turned into high survival rate after pre-exposure to 59 kPa, for which molecular explanation were also found. The pO2 of 59 kPa (very high altitude zone elicits systemic energy and redox homeostatic processes by modulating the STAT3-RXR-Nrf2 trio. Finally we posit the various processes downstream of STAT3-RXR-Nrf2 and the plasma proteins that can be used to ascertain the redox status of an individual. Keywords: STAT3, RXR, Nrf2, Network biology, Cytoskeleton, Redox homeostasis, Energy

Polyarene mediators for mediated redox flow battery

Science.gov (United States)

Delnick, Frank M.; Ingersoll, David; Liang, Chengdu

2018-01-02

The fundamental charge storage mechanisms in a number of currently studied high energy redox couples are based on intercalation, conversion, or displacement reactions. With exception to certain metal-air chemistries, most often the active redox materials are stored physically in the electrochemical cell stack thereby lowering the practical gravimetric and volumetric energy density as a tradeoff to achieve reasonable power density. In a general embodiment, a mediated redox flow battery includes a series of secondary organic molecules that form highly reduced anionic radicals as reaction mediator pairs for the reduction and oxidation of primary high capacity redox species ex situ from the electrochemical cell stack. Arenes are reduced to stable anionic radicals that in turn reduce a primary anode to the charged state. The primary anode is then discharged using a second lower potential (more positive) arene. Compatible separators and solvents are also disclosed herein.

Insights in the electronic structure and redox reaction energy in LiFePO4 battery material from an accurate Tran-Blaha modified Becke Johnson potential

International Nuclear Information System (INIS)

Araujo, Rafael B.; Almeida, J. de S; Ferreira da Silva, A.; Ahuja, Rajeev

2015-01-01

The main goals of this paper are to investigate the accuracy of the Tran-Blaha modified Becke Johnson (TB-mBJ) potential to predict the electronic structure of lithium iron phosphate and the related redox reaction energy with the lithium deintercalation process. The computed electronic structures show that the TB-mBJ method is able to partially localize Fe-3d electrons in LiFePO 4 and FePO 4 which usually is a problem for the generalized gradient approximation (GGA) due to the self interaction error. The energy band gap is also improved by the TB-mBJ calculations in comparison with the GGA results. It turned out, however, that the redox reaction energy evaluated by the TB-mBJ technique is not in good agreement with the measured one. It is speculated that this disagreement in the computed redox energy and the experimental value is due to the lack of a formal expression to evaluate the exchange and correlation energy. Therefore, the TB-mBJ is an efficient method to improve the prediction of the electronic structures coming form the standard GGA functional in LiFePO 4 and FePO 4 . However, it does not appear to have the same efficiency for evaluating the redox reaction energies for the investigated system

Mesoporous tungsten oxynitride as electrocatalyst for promoting redox reactions of vanadium redox couple and performance of vanadium redox flow battery

Science.gov (United States)

Lee, Wonmi; Jo, Changshin; Youk, Sol; Shin, Hun Yong; Lee, Jinwoo; Chung, Yongjin; Kwon, Yongchai

2018-01-01

For enhancing the performance of vanadium redox flow battery (VRFB), a sluggish reaction rate issue of V2+/V3+ redox couple evaluated as the rate determining reaction should be addressed. For doing that, mesoporous tungsten oxide (m-WO3) and oxyniride (m-WON) structures are proposed as the novel catalysts, while m-WON is gained by NH3 heat treatment of m-WO3. Their specific surface area, crystal structure, surface morphology and component analysis are measured using BET, XRD, TEM and XPS, while their catalytic activity for V2+/V3+ redox reaction is electrochemically examined. As a result, the m-WON shows higher peak current, smaller peak potential difference, higher electron transfer rate constant and lower charge transfer resistance than other catalysts, like the m-WO3, WO3 nanoparticle and mesoporous carbon, proving that it is superior catalyst. Regarding the charge-discharge curve tests, the VRFB single cell employing the m-WON demonstrates high voltage and energy efficiencies, high specific capacity and low capacity loss rate. The excellent results of m-WON are due to the reasons like (i) reduced energy band gap, (ii) reaction familiar surface functional groups and (ii) greater electronegativity.

Organic molecules as tools to control the growth, surface structure, and redox activity of colloidal quantum dots.

Science.gov (United States)

Weiss, Emily A

2013-11-19

In order to achieve efficient and reliable technology that can harness solar energy, the behavior of electrons and energy at interfaces between different types or phases of materials must be understood. Conversion of light to chemical or electrical potential in condensed phase systems requires gradients in free energy that allow the movement of energy or charge carriers and facilitate redox reactions and dissociation of photoexcited states (excitons) into free charge carriers. Such free energy gradients are present at interfaces between solid and liquid phases or between inorganic and organic materials. Nanostructured materials have a higher density of these interfaces than bulk materials. Nanostructured materials, however, have a structural and chemical complexity that does not exist in bulk materials, which presents a difficult challenge: to lower or eliminate energy barriers to electron and energy flux that inevitably result from forcing different materials to meet in a spatial region of atomic dimensions. Chemical functionalization of nanostructured materials is perhaps the most versatile and powerful strategy for controlling the potential energy landscape of their interfaces and for minimizing losses in energy conversion efficiency due to interfacial structural and electronic defects. Colloidal quantum dots are semiconductor nanocrystals synthesized with wet-chemical methods and coated in organic molecules. Chemists can use these model systems to study the effects of chemical functionalization of nanoscale organic/inorganic interfaces on the optical and electronic properties of a nanostructured material, and the behavior of electrons and energy at interfaces. The optical and electronic properties of colloidal quantum dots have an intense sensitivity to their surface chemistry, and their organic adlayers make them dispersible in solvent. This allows researchers to use high signal-to-noise solution-phase spectroscopy to study processes at interfaces. In this

The developments and challenges of cerium half-cell in zinc–cerium redox flow battery for energy storage

International Nuclear Information System (INIS)

Xie, Zhipeng; Liu, Qingchao; Chang, Zhiwen; Zhang, Xinbo

2013-01-01

Zinc–cerium redox flow batteries (ZCBs) are emerging as a very promising new technology with the potential to store a large amount of energy economically and efficiently, thanking to its highest thermodynamic open-circuit cell voltage among all the currently studied aqueous redox flow batteries. However, there are numerous scientific and technical challenges that must be overcome if this alluring promise is to turn into reality, from designing the battery structure, to optimizing the electrolyte compositions and elucidating the complex chemical reactions that occur during charge and discharge. This review article is the first summary of the most significant developments and challenges of cerium half-cell and the current understanding of their chemistry. We are certain that this review will be of great interest to audience over a broad range, especially in fields of energy storage, electrochemistry, and chemical engineering

Metformin selectively targets redox control of complex I energy transduction

Directory of Open Access Journals (Sweden)

Amy R. Cameron

2018-04-01

Full Text Available Many guanide-containing drugs are antihyperglycaemic but most exhibit toxicity, to the extent that only the biguanide metformin has enjoyed sustained clinical use. Here, we have isolated unique mitochondrial redox control properties of metformin that are likely to account for this difference. In primary hepatocytes and H4IIE hepatoma cells we found that antihyperglycaemic diguanides DG5-DG10 and the biguanide phenformin were up to 1000-fold more potent than metformin on cell signalling responses, gluconeogenic promoter expression and hepatocyte glucose production. Each drug inhibited cellular oxygen consumption similarly but there were marked differences in other respects. All diguanides and phenformin but not metformin inhibited NADH oxidation in submitochondrial particles, indicative of complex I inhibition, which also corresponded closely with dehydrogenase activity in living cells measured by WST-1. Consistent with these findings, in isolated mitochondria, DG8 but not metformin caused the NADH/NAD+ couple to become more reduced over time and mitochondrial deterioration ensued, suggesting direct inhibition of complex I and mitochondrial toxicity of DG8. In contrast, metformin exerted a selective oxidation of the mitochondrial NADH/NAD+ couple, without triggering mitochondrial deterioration. Together, our results suggest that metformin suppresses energy transduction by selectively inducing a state in complex I where redox and proton transfer domains are no longer efficiently coupled. Keywords: Diabetes, Metformin, Mitochondria, NADH, NAD+

Redox electrodes comprised of polymer-modified carbon nanomaterials

Science.gov (United States)

Roberts, Mark; Emmett, Robert; Karakaya, Mehmet; Podila, Ramakrishna; Rao, Apparao; Clemson Physics Team; Clemson Chemical Engineering Team

2013-03-01

A shift in how we generate and use electricity requires new energy storage materials and systems compatible with hybrid electric transportation and the integration of renewable energy sources. Supercapacitors provide a solution to these needs by combining the high power, rapid switching, and exceptional cycle life of a capacitor with the high energy density of a battery. Our research brings together nanotechnology and materials chemistry to address the limitations of electrode materials. Paper electrodes fabricated with various forms of carbon nanomaterials, such as nanotubes, are modified with redox-polymers to increase the electrode's energy density while maintaining rapid discharge rates. In these systems, the carbon nanomaterials provide the high surface area, electrical conductivity, nanoscale and porosity, while the redox polymers provide a mechanism for charge storage through Faradaic charge transfer. The design of redox polymers and their incorporation into nanomaterial electrodes will be discussed with a focus on enabling high power and high energy density electrodes.

Flexible and semi-transparent thermoelectric energy harvesters from low cost bulk silicon (100)

KAUST Repository

Sevilla, Galo T.

2013-07-09

Flexible and semi-transparent high performance thermoelectric energy harvesters are fabricated on low cost bulk mono-crystalline silicon (100) wafers. The released silicon is only 3.6% as thick as bulk silicon reducing the thermal loss significantly and generating nearly 30% more output power than unpeeled harvesters. This generic batch processing is a pragmatic way of transforming traditional silicon circuitry for extremely deformable high-performance integrated electronics. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flexible and semi-transparent thermoelectric energy harvesters from low cost bulk silicon (100)

KAUST Repository

Sevilla, Galo T.; Inayat, Salman Bin; Rojas, Jhonathan Prieto; Hussain, Aftab M.; Hussain, Muhammad Mustafa

2013-01-01

Flexible and semi-transparent high performance thermoelectric energy harvesters are fabricated on low cost bulk mono-crystalline silicon (100) wafers. The released silicon is only 3.6% as thick as bulk silicon reducing the thermal loss significantly and generating nearly 30% more output power than unpeeled harvesters. This generic batch processing is a pragmatic way of transforming traditional silicon circuitry for extremely deformable high-performance integrated electronics. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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-Br 2 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 H 2 O, 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, (FcN 2 Br 2 , 3.1 M in H 2 O, 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 FcN 2 Br 2 /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.

Redox Stable Anodes for Solid Oxide Fuel Cells

Directory of Open Access Journals (Sweden)

Guoliang eXiao

2014-06-01

Full Text Available Solid oxide fuel cells (SOFCs can convert chemical energy from the fuel directly to electrical energy with high efficiency and fuel flexibility. Ni-based cermets have been the most widely adopted anode for SOFCs. However, the conventional Ni-based anode has low tolerance to sulfur-contamination, is vulnerable to deactivation by carbon build-up (coking from direct oxidation of hydrocarbon fuels, and suffers volume instability upon redox cycling. Among these limitations, the redox instability of the anode is particularly important and has been intensively studied since the SOFC anode may experience redox cycling during fuel cell operations even with the ideal pure hydrogen as the fuel. This review aims to highlight recent progresses on improving redox stability of the conventional Ni-based anode through microstructure optimization and exploration of alternative ceramic-based anode materials.

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.

Redox flow batteries having multiple electroactive elements

Energy Technology Data Exchange (ETDEWEB)

Wang, Wei; Li, Liyu; Yang, Zhenguo; Nie, Zimin

2018-05-01

Introducing multiple redox reactions with a suitable voltage range can improve the energy density of redox flow battery (RFB) systems. One example includes RFB systems utilizing multiple redox pairs in the positive half cell, the negative half cell, or in both. Such RFB systems can have a negative electrolyte, a positive electrolyte, and a membrane between the negative electrolyte and the positive electrolyte, in which at least two electrochemically active elements exist in the negative electrolyte, the positive electrolyte, or both.

Scaling laws in high-energy inverse compton scattering. II. Effect of bulk motions

International Nuclear Information System (INIS)

Nozawa, Satoshi; Kohyama, Yasuharu; Itoh, Naoki

2010-01-01

We study the inverse Compton scattering of the CMB photons off high-energy nonthermal electrons. We extend the formalism obtained by the previous paper to the case where the electrons have nonzero bulk motions with respect to the CMB frame. Assuming the power-law electron distribution, we find the same scaling law for the probability distribution function P 1,K (s) as P 1 (s) which corresponds to the zero bulk motions, where the peak height and peak position depend only on the power-index parameter. We solved the rate equation analytically. It is found that the spectral intensity function also has the same scaling law. The effect of the bulk motions to the spectral intensity function is found to be small. The present study will be applicable to the analysis of the x-ray and gamma-ray emission models from various astrophysical objects with nonzero bulk motions such as radio galaxies and astrophysical jets.

Solvent effect on redox properties of hexanethiolate monolayer-protected gold nanoclusters.

Science.gov (United States)

Su, Bin; Zhang, Meiqin; Shao, Yuanhua; Girault, Hubert H

2006-11-02

The capacitance of monolayer-protected gold nanoclusters (MPCs), C(MPC), in solution has been theoretically reconsidered from an electrostatic viewpoint, in which an MPC is considered as an isolated charged sphere within two dielectric layers, the intrinsic coating monolayer, and the bulk solvent. The model predicts that the bulk solvent provides an important contribution to C(MPC) and influences the redox properties of MPCs. This theoretical prediction is then examined experimentally by comparing the redox properties of MPCs in four organic solvents: 1,2-dichloroethane (DCE), dichloromethane (DCM), chlorobenzene (CB), and toluene (TOL), in all of which MPCs have excellent solubility. Furthermore, this set of organic solvents features a dielectric constant in a range from 10.37 (DCE) to 2.38 (TOL), which is wide enough to probe the solvent effect. In these organic solvents, tetrahexylammonium bis(trifluoromethylsulfonyl)imide (THATf2N) is used as the supporting electrolyte. Cyclic and differential pulse voltammetric results provide concrete evidence that, despite the monolayer protection, the solvent plays a significant effect on the properties of MPCs in solution.

Study to establish cost projections for production of Redox chemicals

Science.gov (United States)

Walther, J. F.; Greco, C. C.; Rusinko, R. N.; Wadsworth, A. L., III

1982-01-01

A cost study of four proposed manufacturing processes for redox chemicals for the NASA REDOX Energy Storage System yielded favorable selling prices in the range $0.99 to $1.91/kg of chromic chloride, anhydrous basis, including ferrous chloride. The prices corresponded to specific energy storage costs from under $9 to $17/kWh. A refined and expanded cost analysis of the most favored process yielded a price estimate corresponding to a storage cost of $11/kWh. The findings supported the potential economic viability of the NASA REDOX system.

Recent developments in organic redox flow batteries: A critical review

Science.gov (United States)

Leung, P.; Shah, A. A.; Sanz, L.; Flox, C.; Morante, J. R.; Xu, Q.; Mohamed, M. R.; Ponce de León, C.; Walsh, F. C.

2017-08-01

Redox flow batteries (RFBs) have emerged as prime candidates for energy storage on the medium and large scales, particularly at the grid scale. The demand for versatile energy storage continues to increase as more electrical energy is generated from intermittent renewable sources. A major barrier in the way of broad deployment and deep market penetration is the use of expensive metals as the active species in the electrolytes. The use of organic redox couples in aqueous or non-aqueous electrolytes is a promising approach to reducing the overall cost in long-term, since these materials can be low-cost and abundant. The performance of such redox couples can be tuned by modifying their chemical structure. In recent years, significant developments in organic redox flow batteries has taken place, with the introduction of new groups of highly soluble organic molecules, capable of providing a cell voltage and charge capacity comparable to conventional metal-based systems. This review summarises the fundamental developments and characterization of organic redox flow batteries from both the chemistry and materials perspectives. The latest advances, future challenges and opportunities for further development are discussed.

Anthraquinone with Tailored Structure for Nonaqueous Metal-Organic Redox Flow Battery

Energy Technology Data Exchange (ETDEWEB)

Wang, Wei; Xu, Wu; Cosimbescu, Lelia; Choi, Daiwon; Li, Liyu; Yang, Zhenguo

2012-06-08

A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of {approx}82% and a specific discharge energy density similar to aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

TEMPOL increases NAD+ and improves redox imbalance in obese mice

Directory of Open Access Journals (Sweden)

Mayumi Yamato

2016-08-01

Full Text Available Continuous energy conversion is controlled by reduction–oxidation (redox processes. NAD+ and NADH represent an important redox couple in energy metabolism. 4-Hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL is a redox-cycling nitroxide that promotes the scavenging of several reactive oxygen species (ROS and is reduced to hydroxylamine by NADH. TEMPOL is also involved in NAD+ production in the ascorbic acid–glutathione redox cycle. We utilized the chemical properties of TEMPOL to investigate the effects of antioxidants and NAD+/NADH modulators on the metabolic imbalance in obese mice. Increases in the NAD+/NADH ratio by TEMPOL ameliorated the metabolic imbalance when combined with a dietary intervention, changing from a high-fat diet to a normal diet. Plasma levels of the superoxide marker dihydroethidium were higher in mice receiving the dietary intervention compared with a control diet, but were normalized with TEMPOL consumption. These findings provide novel insights into redox regulation in obesity.

Energy-depth relation of electrons in bulk targets by Monte-Carlo calculations

International Nuclear Information System (INIS)

Gaber, M.; Fitting, H.J.

1984-01-01

Monte-Carlo calculations are used to calculate the energy of penetrating electrons as a function of the depth in thick targets of Ti, Fe, Cu, As, In, and Au. It is shown that the mean energy ratio anti E(z)/E 0 decays exponentially with depth z and depends on the backscattering coefficient eta/sub B/ of the bulk material and the maximum range R(E 0 ) of the primary electrons with initial energy E 0 . Thereby a normalized plot anti E/E 0 as a function of the reduced depth z/R becomes possible. (author)

Emission-energy dependence of ultrafast P-emission decay in ZnO from bulk to nanofilm

International Nuclear Information System (INIS)

Wakaiki, Shuji; Ichida, Hideki; Bamba, Motoaki; Kawase, Toshiki; Kawakami, Masaki; Mizoguchi, Kohji; Kim, DaeGwi; Nakayama, Masaaki; Kanematsu, Yasuo

2014-01-01

We have performed time-resolved photoluminescence (PL) spectroscopy for ZnO thin films with thicknesses of 90, 460, and 2800 nm under intense excitation condition. We clearly observed the P emission due to inelastic exciton–exciton scattering. It was found that, in the 460- and 2800-nm thick samples, the decay time of the P emission considerably depends on the detection energy inversely proportional to the group velocity of the polariton in a bulk crystal with each factor of proportionality. In contrast, the energy dependence is less remarkable in the 90-nm thick sample. The decay times are basically shortened with a decrease in the film thickness. The thickness dependence of the P-emission-decay profiles is explained by considering the crossover from the polariton modes in the 2800-nm thick sample (bulk-like film) to the exciton-/photon-like modes in the 90-nm thick sample (nanofilm). - Highlights: • We clearly observed the P-PL dynamics due to inelastic exciton–exciton scattering. • The P-PL decay times are basically shortened with a decrease in the film thickness. • The P-PL decay time depends on the detection energy in the bulk-like sample. • The energy dependence of the P-PL decay time almost disappears in the 90-nm sample. • The thickness dependence is explained by the crossover between exciton and photon

Emission-energy dependence of ultrafast P-emission decay in ZnO from bulk to nanofilm

Energy Technology Data Exchange (ETDEWEB)

Wakaiki, Shuji, E-mail: s.wakaiki@mls.eng.osaka-u.ac.jp [Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871 (Japan); Ichida, Hideki [Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871 (Japan); Science and Technology Entrepreneurship Laboratory, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871 (Japan); Bamba, Motoaki [Department of Physics, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043 (Japan); Kawase, Toshiki; Kawakami, Masaki [Department of Applied Physics, Graduate School of Engineering, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan); Mizoguchi, Kohji [Department of Physical Science, Graduate School of Science, Osaka Prefecture University, 1-1 Gakuen, Naka-ku, Sakai, Osaka 599-8531 (Japan); Kim, DaeGwi; Nakayama, Masaaki [Department of Applied Physics, Graduate School of Engineering, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan); Kanematsu, Yasuo [Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871 (Japan); Science and Technology Entrepreneurship Laboratory, Osaka University, 2-1 Yamada-oka, Suita, Osaka 565-0871 (Japan)

2014-08-01

We have performed time-resolved photoluminescence (PL) spectroscopy for ZnO thin films with thicknesses of 90, 460, and 2800 nm under intense excitation condition. We clearly observed the P emission due to inelastic exciton–exciton scattering. It was found that, in the 460- and 2800-nm thick samples, the decay time of the P emission considerably depends on the detection energy inversely proportional to the group velocity of the polariton in a bulk crystal with each factor of proportionality. In contrast, the energy dependence is less remarkable in the 90-nm thick sample. The decay times are basically shortened with a decrease in the film thickness. The thickness dependence of the P-emission-decay profiles is explained by considering the crossover from the polariton modes in the 2800-nm thick sample (bulk-like film) to the exciton-/photon-like modes in the 90-nm thick sample (nanofilm). - Highlights: • We clearly observed the P-PL dynamics due to inelastic exciton–exciton scattering. • The P-PL decay times are basically shortened with a decrease in the film thickness. • The P-PL decay time depends on the detection energy in the bulk-like sample. • The energy dependence of the P-PL decay time almost disappears in the 90-nm sample. • The thickness dependence is explained by the crossover between exciton and photon.

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.

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization and assessment of novel bulk storage technologies : a study for the DOE Energy Storage Systems program.

Energy Technology Data Exchange (ETDEWEB)

Huff, Georgianne; Tong, Nellie (KEMA Consulting, Fairfax, VA); Fioravanti, Richard (KEMA Consulting, Fairfax, VA); Gordon, Paul (Sentech/SRA International, Bethesda, MD); Markel, Larry (Sentech/SRA International, Bethesda, MD); Agrawal, Poonum (Sentech/SRA International, Bethesda, MD); Nourai, Ali (KEMA Consulting, Fairfax, VA)

2011-04-01

This paper reports the results of a high-level study to assess the technological readiness and technical and economic feasibility of 17 novel bulk energy storage technologies. The novel technologies assessed were variations of either pumped storage hydropower (PSH) or compressed air energy storage (CAES). The report also identifies major technological gaps and barriers to the commercialization of each technology. Recommendations as to where future R&D efforts for the various technologies are also provided based on each technology's technological readiness and the expected time to commercialization (short, medium, or long term). The U.S. Department of Energy (DOE) commissioned this assessment of novel concepts in large-scale energy storage to aid in future program planning of its Energy Storage Program. The intent of the study is to determine if any new but still unproven bulk energy storage concepts merit government support to investigate their technical and economic feasibility or to speed their commercialization. The study focuses on compressed air energy storage (CAES) and pumped storage hydropower (PSH). It identifies relevant applications for bulk storage, defines the associated technical requirements, characterizes and assesses the feasibility of the proposed new concepts to address these requirements, identifies gaps and barriers, and recommends the type of government support and research and development (R&D) needed to accelerate the commercialization of these technologies.

Redox regulation in photosynthetic organisms: signaling, acclimation, and practical implications.

Science.gov (United States)

Foyer, Christine H; Noctor, Graham

2009-04-01

Reactive oxygen species (ROS) have multifaceted roles in the orchestration of plant gene expression and gene-product regulation. Cellular redox homeostasis is considered to be an "integrator" of information from metabolism and the environment controlling plant growth and acclimation responses, as well as cell suicide events. The different ROS forms influence gene expression in specific and sometimes antagonistic ways. Low molecular antioxidants (e.g., ascorbate, glutathione) serve not only to limit the lifetime of the ROS signals but also to participate in an extensive range of other redox signaling and regulatory functions. In contrast to the low molecular weight antioxidants, the "redox" states of components involved in photosynthesis such as plastoquinone show rapid and often transient shifts in response to changes in light and other environmental signals. Whereas both types of "redox regulation" are intimately linked through the thioredoxin, peroxiredoxin, and pyridine nucleotide pools, they also act independently of each other to achieve overall energy balance between energy-producing and energy-utilizing pathways. This review focuses on current knowledge of the pathways of redox regulation, with discussion of the somewhat juxtaposed hypotheses of "oxidative damage" versus "oxidative signaling," within the wider context of physiological function, from plant cell biology to potential applications.

Interplay between bulk medium evolution and (D)GLV energy loss

International Nuclear Information System (INIS)

Molnar, Denes; Sun, Deke

2014-01-01

We study the consistency between high-p T nuclear suppression (R AA ) and elliptic flow (v 2 ) using Gyulassy–Levai–Vitev (GLV) energy loss or a simpler power-law dE/dL formula, for a variety of bulk evolution models. The results generally confirm our earlier work [1] that found suppressed elliptic flow for transversely expanding media. One exception is the set of hydrodynamic solutions used recently [2] by Betz and Gyulassy, which give significantly higher v 2 but unfortunately assume unrealistic bag-model equation of state. On the other hand, we show that covariant treatment of energy loss introduces an interplay between jet direction and hydrodynamic flow of the medium, which largely counteracts elliptic flow suppression caused by transverse expansion

Redox Species-Based Electrolytes for Advanced Rechargeable Lithium Ion Batteries

KAUST Repository

Ming, Jun

2016-08-15

Seeking high-capacity cathodes has become an intensive effort in lithium ion battery research; however, the low energy density still remains a major issue for sustainable handheld devices and vehicles. Herein, we present a new strategy of integrating a redox species-based electrolyte in batteries to boost their performance. Taking the olivine LiFePO4-based battery as an example, the incorporation of redox species (i.e., polysulfide of Li2S8) in the electrolyte results in much lower polarization and superior stability, where the dissociated Li+/Sx2– can significantly speed up the lithium diffusion. More importantly, the presence of the S82–/S2– redox reaction further contributes extra capacity, making a completely new LiFePO4/Li2Sx hybrid battery with a high energy density of 1124 Wh kgcathode–1 and a capacity of 442 mAh gcathode–1. The marriage of appropriate redox species in an electrolyte for a rechargeable battery is an efficient and scalable approach for obtaining higher energy density storage devices.

Carbon-free Solid Dispersion LiCoO2 Redox Couple Characterization and Electrochemical Evaluation for All Solid Dispersion Redox Flow Batteries

International Nuclear Information System (INIS)

Qi, Zhaoxiang; Liu, Aaron L.; Koenig, Gary M.

2017-01-01

Highlights: • LiCoO 2 particles can be cycled in carbon-free and binder-free coin cells. • A carbon-free LiCoO 2 suspension is electrochemically oxidized and reduced. • Comparable size LiCoO 2 and Li 4 Ti 5 O 12 suspensions have similar rheological properties. • First demonstration of redox couples with solid suspensions for both electrodes. - Abstract: Semi-solid flow batteries have been reported to have among the highest energy densities for redox flow batteries, however, they rely on percolated carbon networks which increase the electrolyte viscosity significantly. We report the first demonstration of carbon-free redox flow couples comprised of dispersed lithium-ion battery active material suspensions, with sub-micrometer LiCoO 2 (LCO) particles at the cathode and Li 4 Ti 5 O 12 (LTO) particles at the anode. Both electrochemical and rheological properties of the LCO suspensions are reported and compared to previous reports for LTO dispersed electrochemical redox couples. An LTO anode and LCO cathode full cell was constructed and reversible electrochemical redox reaction of the dispersed particles was successfully demonstrated. This carbon-free dispersed lithium-ion active material full cell provides a proof-of-concept for a system that lies between the relatively high viscosity semi-solid flow cells with percolated carbon networks and the relatively low energy density conventional flow cells comprised of dissolved transition metals, providing a system for future study of the trade-off between energy density and viscosity for electrochemical flow cells that rely on solid active materials.

Anthraquinone with tailored structure for a nonaqueous metal-organic redox flow battery.

Science.gov (United States)

Wang, Wei; Xu, Wu; Cosimbescu, Lelia; Choi, Daiwon; Li, Liyu; Yang, Zhenguo

2012-07-07

A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of ~82% and a specific discharge energy density similar to those of aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

The Redox Code.

Science.gov (United States)

Jones, Dean P; Sies, Helmut

2015-09-20

The redox code is a set of principles that defines the positioning of the nicotinamide adenine dinucleotide (NAD, NADP) and thiol/disulfide and other redox systems as well as the thiol redox proteome in space and time in biological systems. The code is richly elaborated in an oxygen-dependent life, where activation/deactivation cycles involving O₂ and H₂O₂ contribute to spatiotemporal organization for differentiation, development, and adaptation to the environment. Disruption of this organizational structure during oxidative stress represents a fundamental mechanism in system failure and disease. Methodology in assessing components of the redox code under physiological conditions has progressed, permitting insight into spatiotemporal organization and allowing for identification of redox partners in redox proteomics and redox metabolomics. Complexity of redox networks and redox regulation is being revealed step by step, yet much still needs to be learned. Detailed knowledge of the molecular patterns generated from the principles of the redox code under defined physiological or pathological conditions in cells and organs will contribute to understanding the redox component in health and disease. Ultimately, there will be a scientific basis to a modern redox medicine.

Surface Redox Chemistry of Immobilized Nanodiamond: Effects of Particle Size and Electrochemical Environment

Science.gov (United States)

Gupta, S.; McDonald, B.; Carrizosa, S. B.

2017-07-01

The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 μm << 1000 nm < 100 nm < 10 nm ≤ 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN) 6 3+ ) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites ( sp 2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox

Bulk superconducting gap of V_3Si studied by low-energy ultrahigh-resolution photoemission spectroscopy

International Nuclear Information System (INIS)

Sato, T.; Souma, S.; Nakayama, K.; Sugawara, K.; Toyota, N.; Takahashi, T.

2016-01-01

Highlights: • We report ultrahigh-resolution photoemission spectroscopy of A15 compound V_3Si. • We found a sharp quasiparticle peak due to superconducting-gap opening. • The surface metallic component is negligibly small in the bulk-sensitive measurement. • We show that V_3Si is a single-gap s-wave superconductor. - Abstract: We have performed low-energy ultrahigh-resolution photoemission spectroscopy (PES) of A15 compound V_3Si with a xenon-plasma discharge lamp to elucidate the bulk superconducting gap. Below the superconducting transition temperature (T_c = 15.9 K), we found a sharp quasiparticle peak at the Fermi level in the PES spectrum. The gap spectrum is well fitted by a single s-wave superconducting-gap function together with a dip structure at ∼30 meV suggestive of a strong electron-phonon coupling. The anomalous in-gap state previously observed in the PES measurement with high-energy photons is absent or negligibly small in the present bulk-sensitive measurement. The present PES result shows that V_3Si is a single-gap s-wave superconductor.

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.

Characterization of PEDOT-Quinone Conducting Redox Polymers for Water Based Secondary Batteries

International Nuclear Information System (INIS)

Sterby, Mia; Emanuelsson, Rikard; Huang, Xiao; Gogoll, Adolf; Strømme, Maria; Sjödin, Martin

2017-01-01

Lithium-ion technologies show great promise to meet the demands that the transition towards renewable energy sources and the electrification of the transport sector put forward. However, concerns regarding lithium-ion batteries, including limited material resources, high energy consumption during production, and flammable electrolytes, necessitate research on alternative technologies for electrochemical energy storage. Organic materials derived from abundant building blocks and with tunable properties, together with water based electrolytes, could provide safe, inexpensive and sustainable alternatives. In this study, two conducting redox polymers based on poly(3,4-ethylenedioxythiophene) (PEDOT) and a hydroquinone pendant group have been synthesized and characterized in an acidic aqueous electrolyte. The polymers were characterized with regards to kinetics, pH dependence, and mass changes during oxidation and reduction, as well as their conductance. Both polymers show redox matching, i.e. the quinone redox reaction occurs within the potential region where the polymer is conducting, and fast redox conversion that involves proton cycling during pendant group redox conversion. These properties make the presented materials promising candidates as electrode materials for water based all-organic batteries.

New holographic dark energy model with constant bulk viscosity in modified f(R,T) gravity theory

Science.gov (United States)

Srivastava, Milan; Singh, C. P.

2018-06-01

The aim of this paper is to study new holographic dark energy (HDE) model in modified f(R,T) gravity theory within the framework of a flat Friedmann-Robertson-Walker model with bulk viscous matter content. It is thought that the negative pressure caused by the bulk viscosity can play the role of dark energy component, and drive the accelerating expansion of the universe. This is the motive of this paper to observe such phenomena with bulk viscosity. In the specific model f(R,T)=R+λ T, where R is the Ricci scalar, T the trace of the energy-momentum tensor and λ is a constant, we find the solution for non-viscous and viscous new HDE models. We analyze new HDE model with constant bulk viscosity, ζ =ζ 0= const. to explain the present accelerated expansion of the universe. We classify all possible scenarios (deceleration, acceleration and their transition) with possible positive and negative ranges of λ over the constraint on ζ 0 to analyze the evolution of the universe. We obtain the solutions of scale factor and deceleration parameter, and discuss the evolution of the universe. We observe the future finite-time singularities of type I and III at a finite time under certain constraints on λ . We also investigate the statefinder and Om diagnostics of the viscous new HDE model to discriminate with other existing dark energy models. In late time the viscous new HDE model approaches to Λ CDM model. We also discuss the thermodynamics and entropy of the model and find that it satisfies the second law of thermodynamics.

Bulk properties of the medium produced in relativistic heavy-ion collisions from the beam energy scan program

Science.gov (United States)

Adamczyk, L.; Adkins, J. K.; Agakishiev, G.; Aggarwal, M. M.; Ahammed, Z.; Ajitanand, N. N.; Alekseev, I.; Anderson, D. M.; Aoyama, R.; Aparin, A.; Arkhipkin, D.; Aschenauer, E. C.; Ashraf, M. U.; Attri, A.; Averichev, G. S.; Bai, X.; Bairathi, V.; Behera, A.; Bellwied, R.; Bhasin, A.; Bhati, A. K.; Bhattarai, P.; Bielcik, J.; Bielcikova, J.; Bland, L. C.; Bordyuzhin, I. G.; Bouchet, J.; Brandenburg, J. D.; Brandin, A. V.; Brown, D.; Bunzarov, I.; Butterworth, J.; Caines, H.; Calderón de la Barca Sánchez, M.; Campbell, J. M.; Cebra, D.; Chakaberia, I.; Chaloupka, P.; Chang, Z.; Chankova-Bunzarova, N.; Chatterjee, A.; Chattopadhyay, S.; Chen, X.; Chen, J. H.; Chen, X.; Cheng, J.; Cherney, M.; Christie, W.; Contin, G.; Crawford, H. J.; Das, S.; De Silva, L. C.; Debbe, R. R.; Dedovich, T. G.; Deng, J.; Derevschikov, A. A.; Didenko, L.; Dilks, C.; Dong, X.; Drachenberg, J. L.; Draper, J. E.; Dunkelberger, L. E.; Dunlop, J. C.; Efimov, L. G.; Elsey, N.; Engelage, J.; Eppley, G.; Esha, R.; Esumi, S.; Evdokimov, O.; Ewigleben, J.; Eyser, O.; Fatemi, R.; Fazio, S.; Federic, P.; Federicova, P.; Fedorisin, J.; Feng, Z.; Filip, P.; Finch, E.; Fisyak, Y.; Flores, C. E.; Fulek, L.; Gagliardi, C. A.; Garand, D.; Geurts, F.; Gibson, A.; Girard, M.; Grosnick, D.; Gunarathne, D. S.; Guo, Y.; Gupta, A.; Gupta, S.; Guryn, W.; Hamad, A. I.; Hamed, A.; Harlenderova, A.; Harris, J. W.; He, L.; Heppelmann, S.; Heppelmann, S.; Hirsch, A.; Hoffmann, G. W.; Horvat, S.; Huang, T.; Huang, B.; Huang, X.; Huang, H. Z.; Humanic, T. J.; Huo, P.; Igo, G.; Jacobs, W. W.; Jentsch, A.; Jia, J.; Jiang, K.; Jowzaee, S.; Judd, E. G.; Kabana, S.; Kalinkin, D.; Kang, K.; Kauder, K.; Ke, H. W.; Keane, D.; Kechechyan, A.; Khan, Z.; Kikoła, D. P.; Kisel, I.; Kisiel, A.; Kochenda, L.; Kocmanek, M.; Kollegger, T.; Kosarzewski, L. K.; Kraishan, A. F.; Kravtsov, P.; Krueger, K.; Kulathunga, N.; Kumar, L.; Kvapil, J.; Kwasizur, J. H.; Lacey, R.; Landgraf, J. M.; Landry, K. D.; Lauret, J.; Lebedev, A.; Lednicky, R.; Lee, J. H.; Li, X.; Li, C.; Li, W.; Li, Y.; Lidrych, J.; Lin, T.; Lisa, M. A.; Liu, H.; Liu, P.; Liu, Y.; Liu, F.; Ljubicic, T.; Llope, W. J.; Lomnitz, M.; Longacre, R. S.; Luo, S.; Luo, X.; Ma, G. L.; Ma, L.; Ma, Y. G.; Ma, R.; Magdy, N.; Majka, R.; Mallick, D.; Margetis, S.; Markert, C.; Matis, H. S.; Meehan, K.; Mei, J. C.; Miller, Z. W.; Minaev, N. G.; Mioduszewski, S.; Mishra, D.; Mizuno, S.; Mohanty, B.; Mondal, M. M.; Morozov, D. A.; Mustafa, M. K.; Nasim, Md.; Nayak, T. K.; Nelson, J. M.; Nie, M.; Nigmatkulov, G.; Niida, T.; Nogach, L. V.; Nonaka, T.; Nurushev, S. B.; Odyniec, G.; Ogawa, A.; Oh, K.; Okorokov, V. A.; Olvitt, D.; Page, B. S.; Pak, R.; Pandit, Y.; Panebratsev, Y.; Pawlik, B.; Pei, H.; Perkins, C.; Pile, P.; Pluta, J.; Poniatowska, K.; Porter, J.; Posik, M.; Poskanzer, A. M.; Pruthi, N. K.; Przybycien, M.; Putschke, J.; Qiu, H.; Quintero, A.; Ramachandran, S.; Ray, R. L.; Reed, R.; Rehbein, M. J.; Ritter, H. G.; Roberts, J. B.; Rogachevskiy, O. V.; Romero, J. L.; Roth, J. D.; Ruan, L.; Rusnak, J.; Rusnakova, O.; Sahoo, N. R.; Sahu, P. K.; Salur, S.; Sandweiss, J.; Saur, M.; Schambach, J.; Schmah, A. M.; Schmidke, W. B.; Schmitz, N.; Schweid, B. R.; Seger, J.; Sergeeva, M.; Seyboth, P.; Shah, N.; Shahaliev, E.; Shanmuganathan, P. V.; Shao, M.; Sharma, A.; Sharma, M. K.; Shen, W. Q.; Shi, Z.; Shi, S. S.; Shou, Q. Y.; Sichtermann, E. P.; Sikora, R.; Simko, M.; Singha, S.; Skoby, M. J.; Smirnov, N.; Smirnov, D.; Solyst, W.; Song, L.; Sorensen, P.; Spinka, H. M.; Srivastava, B.; Stanislaus, T. D. S.; Strikhanov, M.; Stringfellow, B.; Sugiura, T.; Sumbera, M.; Summa, B.; Sun, Y.; Sun, X. M.; Sun, X.; Surrow, B.; Svirida, D. N.; Tang, A. H.; Tang, Z.; Taranenko, A.; Tarnowsky, T.; Tawfik, A.; Thäder, J.; Thomas, J. H.; Timmins, A. R.; Tlusty, D.; Todoroki, T.; Tokarev, M.; Trentalange, S.; Tribble, R. E.; Tribedy, P.; Tripathy, S. K.; Trzeciak, B. A.; Tsai, O. D.; Ullrich, T.; Underwood, D. G.; Upsal, I.; Van Buren, G.; van Nieuwenhuizen, G.; Vasiliev, A. N.; Videbæk, F.; Vokal, S.; Voloshin, S. A.; Vossen, A.; Wang, G.; Wang, Y.; Wang, F.; Wang, Y.; Webb, J. C.; Webb, G.; Wen, L.; Westfall, G. D.; Wieman, H.; Wissink, S. W.; Witt, R.; Wu, Y.; Xiao, Z. G.; Xie, W.; Xie, G.; Xu, J.; Xu, N.; Xu, Q. H.; Xu, Y. F.; Xu, Z.; Yang, Y.; Yang, Q.; Yang, C.; Yang, S.; Ye, Z.; Ye, Z.; Yi, L.; Yip, K.; Yoo, I.-K.; Yu, N.; Zbroszczyk, H.; Zha, W.; Zhang, Z.; Zhang, X. P.; Zhang, J. B.; Zhang, S.; Zhang, J.; Zhang, Y.; Zhang, J.; Zhang, S.; Zhao, J.; Zhong, C.; Zhou, L.; Zhou, C.; Zhu, X.; Zhu, Z.; Zyzak, M.; STAR Collaboration

2017-10-01

We present measurements of bulk properties of the matter produced in Au+Au collisions at √{sN N}=7.7 ,11.5 ,19.6 ,27 , and 39 GeV using identified hadrons (π±, K±, p , and p ¯) from the STAR experiment in the Beam Energy Scan (BES) Program at the Relativistic Heavy Ion Collider (RHIC). Midrapidity (|y |<0.1 ) results for multiplicity densities d N /d y , average transverse momenta 〈pT〉 , and particle ratios are presented. The chemical and kinetic freeze-out dynamics at these energies are discussed and presented as a function of collision centrality and energy. These results constitute the systematic measurements of bulk properties of matter formed in heavy-ion collisions over a broad range of energy (or baryon chemical potential) at RHIC.

Redox fronts

International Nuclear Information System (INIS)

Chapman, N.; McKinley, I.; Shea, M.; Smellie, J.

1993-01-01

This article describes the investigations of redox fronts performed at the Osamu Utsumi mine. Results obtained by modelling groups on the rate of movement of the redox fronts and on the chemical reactions involved are discussed. Some of the most important rockwater interactions which occur at redox fronts can be modelled reasonably well but the complex redox chemistry of elements like sulphur is poorly simulated. The observed enrichment of many trace elements close to the redox fronts could be of significance for high-level waste repositories, but cannot be quantified by existing models. (author) 6 figs., 1 tab

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

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 photoelect......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...

Liquid Quinones for Solvent-Free Redox Flow Batteries.

Science.gov (United States)

Shimizu, Akihiro; Takenaka, Keisuke; Handa, Naoyuki; Nokami, Toshiki; Itoh, Toshiyuki; Yoshida, Jun-Ichi

2017-11-01

Liquid benzoquinone and naphthoquinone having diethylene glycol monomethyl ether groups are designed and synthesized as redox active materials that dissolve supporting electrolytes. The Li-ion batteries based on the liquid quinones using LiBF 4 /PC show good performance in terms of voltage, capacity, energy efficiency, and cyclability in both static and flow modes. A battery is constructed without using intentionally added organic solvent, and its high energy density (264 W h L -1 ) demonstrates the potential of solvent-free organic redox flow batteries using liquid active materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Managing the cellular redox hub in photosynthetic organisms.

Science.gov (United States)

Foyer, Christine H; Noctor, Graham

2012-02-01

Light-driven redox chemistry is a powerful source of redox signals that has a decisive input into transcriptional control within the cell nucleus. Like photosynthetic electron transport pathways, the respiratory electron transport chain exerts a profound control over gene function, in order to balance energy (reductant and ATP) supply with demand, while preventing excessive over-reduction or over-oxidation that would be adversely affect metabolism. Photosynthetic and respiratory redox chemistries are not merely housekeeping processes but they exert a controlling influence over every aspect of plant biology, participating in the control of gene transcription and translation, post-translational modifications and the regulation of assimilatory reactions, assimilate partitioning and export. The number of processes influenced by redox controls and signals continues to increase as do the components that are recognized participants in the associated signalling pathways. A step change in our understanding of the overall importance of the cellular redox hub to plant cells has occurred in recent years as the complexity of the management of the cellular redox hub in relation to metabolic triggers and environmental cues has been elucidated. This special issue describes aspects of redox regulation and signalling at the cutting edge of current research in this dynamic and rapidly expanding field. © 2011 Blackwell Publishing Ltd.

Materials and Systems for Organic Redox Flow Batteries: Status and Challenges

Energy Technology Data Exchange (ETDEWEB)

Wei, Xiaoliang [Joint Center for Energy Storage Research (JCESR), Argonne, Illinois 60439, United States; Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Pan, Wenxiao [Department; Duan, Wentao [Joint Center for Energy Storage Research (JCESR), Argonne, Illinois 60439, United States; Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Hollas, Aaron [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Yang, Zheng [Joint Center for Energy Storage Research (JCESR), Argonne, Illinois 60439, United States; Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Li, Bin [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Nie, Zimin [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Liu, Jun [Joint Center for Energy Storage Research (JCESR), Argonne, Illinois 60439, United States; Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Reed, David [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Wang, Wei [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States; Sprenkle, Vincent [Energy & amp, Environment Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States

2017-08-14

Redox flow batteries are propitious stationary energy storage technologies with exceptional scalability and flexibility to improve the stability, efficiency and sustainability of our power grid. The redox-active materials are the central component to RFBs for achieving high energy density and good cyclability. Traditional inorganic-based materials encounter critical technical and economic limitations such as low solubility, inferior electrochemical activity, and high cost. Redox-active organic materials (ROMs) are promising alternative “green” candidates to push the boundaries of energy storage because of the significant advantages of molecular diversity, structural tailorability, and natural abundance. Here the recent development of a variety of ROM families and associated battery designs in both aqueous and nonaqueous electrolytes are reviewed. Moreover, the critical challenges and potential research opportunities for developing practically relevant organic flow batteries are discussed.

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). Published by Elsevier B.V.

Polymersomes containing iron sulfide (FeS) as primordial cell model : for the investigation of energy providing redox reactions.

Science.gov (United States)

Alpermann, Theodor; Rüdel, Kristin; Rüger, Ronny; Steiniger, Frank; Nietzsche, Sandor; Filiz, Volkan; Förster, Stephan; Fahr, Alfred; Weigand, Wolfgang

2011-04-01

According to Wächtershäuser's "Iron-Sulfur-World" one major requirement for the development of life on the prebiotic Earth is compartmentalization. Vesicles spontaneously formed from amphiphilic components containing a specific set of molecules including sulfide minerals may have lead to the first autotrophic prebiotic units. The iron sulfide minerals may have been formed by geological conversions in the environment of deep-sea volcanos (black smokers), which can be observed even today. Wächtershäuser postulated the evolution of chemical pathways as fundamentals of the origin of life on earth. In contrast to the classical Miller-Urey experiment, depending on external energy sources, the "Iron-Sulfur-World" is based on the catalytic and energy reproducing redox system FeS+H2S-->FeS2+H2. The energy release out of this redox reaction (∆RG°=-38 kJ/mol, pH 0) could be the cause for the subsequent synthesis of complex organic molecules and the precondition for the development of more complex units similar to cells known today. Here we show the possibility for precipitating iron sulfide inside vesicles composed of amphiphilic block-copolymers as a model system for a first prebiotic unit. Our findings could be an indication for a chemoautotrophic FeS based origin of life.

Redox behaviors of iron by absorption spectroscopy and redox potential measurement

International Nuclear Information System (INIS)

Oh, Jae Yong

2010-02-01

This work is performed to study the redox (reduction/oxidation) behaviors of iron in aqueous system by a combination of absorption spectroscopy and redox potential measurements. There are many doubts on redox potential measurements generally showing low accuracies and high uncertainties. In the present study, redox potentials are measured by utilizing various redox electrodes such as Pt, Au, Ag, and glassy carbon (GC) electrodes. Measured redox potentials are compared with calculated redox potentials based on the chemical oxidation speciation of iron and thermodynamic data by absorption spectroscopy, which provides one of the sensitive and selective spectroscopic methods for the chemical speciation of Fe(II/III). From the comparison analyses, redox potential values measured by the Ag redox electrode are fairly consistent with those calculated by the chemical aqueous speciation of iron in the whole system. In summary, the uncertainties of measured redox potentials are closely related with the total Fe concentration and affected by the formation of mixed potentials due to Fe(III) precipitates in the pH range of 6 ∼ 9 beyond the solubility of Fe(III), whilst being independent of the initially prepared concentration ratios between Fe(II) and Fe(III)

A Sustainable Redox-Flow Battery with an Aluminum-Based, Deep-Eutectic-Solvent Anolyte.

Science.gov (United States)

Zhang, Changkun; Ding, Yu; Zhang, Leyuan; Wang, Xuelan; Zhao, Yu; Zhang, Xiaohong; Yu, Guihua

2017-06-19

Nonaqueous redox-flow batteries are an emerging energy storage technology for grid storage systems, but the development of anolytes has lagged far behind that of catholytes due to the major limitations of the redox species, which exhibit relatively low solubility and inadequate redox potentials. Herein, an aluminum-based deep-eutectic-solvent is investigated as an anolyte for redox-flow batteries. The aluminum-based deep-eutectic solvent demonstrated a significantly enhanced concentration of circa 3.2 m in the anolyte and a relatively low redox potential of 2.2 V vs. Li + /Li. The electrochemical measurements highlight that a reversible volumetric capacity of 145 Ah L -1 and an energy density of 189 Wh L -1 or 165 Wh kg -1 have been achieved when coupled with a I 3 - /I - catholyte. The prototype cell has also been extended to the use of a Br 2 -based catholyte, exhibiting a higher cell voltage with a theoretical energy density of over 200 Wh L -1 . The synergy of highly abundant, dendrite-free, multi-electron-reaction aluminum anodes and environmentally benign deep-eutectic-solvent anolytes reveals great potential towards cost-effective, sustainable redox-flow batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Topological energy conversion through the bulk or the boundary of driven systems

Science.gov (United States)

Peng, Yang; Refael, Gil

2018-04-01

Combining physical and synthetic dimensions allows a controllable realization and manipulation of high-dimensional topological states. In our work, we introduce two quasiperiodically driven one-dimensional systems which enable tunable topological energy conversion between different driving sources. Using three drives, we realize a four-dimensional quantum Hall state which allows energy conversion between two of the drives within the bulk of the one-dimensional system. With only two drives, we achieve energy conversion between the two at the edge of the chain. Both effects are a manifestation of the effective axion electrodynamics in a three-dimensional time-reversal-invariant topological insulator. Furthermore, we explore the effects of disorder and commensurability of the driving frequencies, and show the phenomena are robust. We propose two experimental platforms, based on semiconductor heterostructures and ultracold atoms in optical lattices, in order to observe the topological energy conversion.

Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy

Science.gov (United States)

Li, Qinghao; Qiao, Ruimin; Wray, L. Andrew; Chen, Jun; Zhuo, Zengqing; Chen, Yanxue; Yan, Shishen; Pan, Feng; Hussain, Zahid; Yang, Wanli

2016-10-01

Most battery positive electrodes operate with a 3d transition-metal (TM) reaction centre. A direct and quantitative probe of the TM states upon electrochemical cycling is valuable for understanding the detailed cycling mechanism and charge diffusion in the electrodes, which is related with many practical parameters of a battery. This review includes a comprehensive summary of our recent demonstrations of five different types of quantitative analysis of the TM states in battery electrodes based on soft x-ray absorption spectroscopy and multiplet calculations. In LiFePO4, a system of a well-known two-phase transformation type, the TM redox could be strictly determined through a simple linear combination of the two end-members. In Mn-based compounds, the Mn states could also be quantitatively evaluated, but a set of reference spectra with all the three possible Mn valences needs to be deliberately selected and considered in the fitting. Although the fluorescence signals suffer the self-absorption distortion, the multiplet calculations could consider the distortion effect, which allows a quantitative determination of the overall Ni oxidation state in the bulk. With the aid of multiplet calculations, one could also achieve a quasi-quantitative analysis of the Co redox evolution in LiCoO2 based on the energy position of the spectroscopic peak. The benefit of multiplet calculations is more important for studying electrode materials with TMs of mixed spin states, as exemplified by the quantitative analysis of the mixed spin Na2-x Fe2(CN)6 system. At the end, we showcase that such quantitative analysis could provide valuable information for optimizing the electrochemical performance of Na0.44MnO2 electrodes for Na-ion batteries. The methodology summarized in this review could be extended to other energy application systems with TM redox centre for detailed analysis, for example, fuel cell and catalytic materials.

Plant redox proteomics

DEFF Research Database (Denmark)

Navrot, Nicolas; Finnie, Christine; Svensson, Birte

2011-01-01

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......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....... 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...

Redox-active media for permeable reactive barriers

International Nuclear Information System (INIS)

Sivavec, T.M.; Mackenzie, P.D.; Horney, D.P.; Baghel, S.S.

1997-01-01

In this paper, three classes of redox-active media are described and evaluated in terms of their long-term effectiveness in treating TCE-contaminated groundwater in permeable reactive zones. Zero-valent iron, in the form of recycled cast iron filings, the first class, has received considerable attention as a reactive media and has been used in about a dozen pilot- and full-scale subsurface wall installations. Criteria used in selecting commercial sources of granular iron, will be discussed. Two other classes of redox-active media that have not yet seen wide use in pilot- or full-scale installations will also be described: Fe(II) minerals and bimetallic systems. Fe(II) minerals, including magnetite (Fe 3 O 4 ), and ferrous sulfide (troilite, FeS), are redox-active and afford TCE reduction rates and product distributions that suggest that they react via a reductive mechanism similar to that which operates in the FeO system. Fe(II) species within the passive oxide layer coating the iron metal may act as electron transfer mediators, with FeO serving as the bulk reductant. Bimetallic systems, the third class of redox-active media, are commonly prepared by plating a second metal onto zero-valent iron (e.g., Ni/Fe and Pd/Fe) and have been shown to accelerate solvent degradation rates relative to untreated iron metal. The long-term effectiveness of this approach, however, has not yet been determined in groundwater treatability tests. The results of a Ni-plated iron column study using site groundwater indicate that a change in reduction mechanism (to catalytic dehydrohalogenation/hydrogenation) accounts for the observed rate enhancement. A significant loss in media reactivity was observed over time, attributable to Ni catalyst deactivation or poisoning. Zero-valent iron systems have not shown similar losses in reactivity in long-term laboratory, pilot or field investigations

The Value of CO2-Geothermal Bulk Energy Storage to Reducing CO2 Emissions Compared to Conventional Bulk Energy Storage Technologies

Science.gov (United States)

Ogland-Hand, J.; Bielicki, J. M.; Buscheck, T. A.

2016-12-01

Sedimentary basin geothermal resources and CO2 that is captured from large point sources can be used for bulk energy storage (BES) in order to accommodate higher penetration and utilization of variable renewable energy resources. Excess energy is stored by pressurizing and injecting CO2 into deep, porous, and permeable aquifers that are ubiquitous throughout the United States. When electricity demand exceeds supply, some of the pressurized and geothermally-heated CO2 can be produced and used to generate electricity. This CO2-BES approach reduces CO2 emissions directly by storing CO2 and indirectly by using some of that CO2 to time-shift over-generation and displace CO2 emissions from fossil-fueled power plants that would have otherwise provided electricity. As such, CO2-BES may create more value to regional electricity systems than conventional pumped hydro energy storage (PHES) or compressed air energy storage (CAES) approaches that may only create value by time-shifting energy and indirectly reducing CO2 emissions. We developed and implemented a method to estimate the value that BES has to reducing CO2 emissions from regional electricity systems. The method minimizes the dispatch of electricity system components to meet exogenous demand subject to various CO2 prices, so that the value of CO2 emissions reductions can be estimated. We applied this method to estimate the performance and value of CO2-BES, PHES, and CAES within real data for electricity systems in California and Texas over the course of a full year to account for seasonal fluctuations in electricity demand and variable renewable resource availability. Our results suggest that the value of CO2-BES to reducing CO2 emissions may be as much as twice that of PHES or CAES and thus CO2-BES may be a more favorable approach to energy storage in regional electricity systems, especially those where the topography is not amenable to PHES or the subsurface is not amenable to CAES.

Enhanced performance of ultracapacitors using redox additive-based electrolytes

Science.gov (United States)

Jain, Dharmendra; Kanungo, Jitendra; Tripathi, S. K.

2018-05-01

Different concentrations of potassium iodide (KI) as redox additive had been added to 1 M sulfuric acid (H2SO4) electrolyte with an aim of enhancing the capacitance and energy density of ultracapacitors via redox reactions at the interfaces of electrode-electrolyte. Ultracapacitors were fabricated using chemically treated activated carbon as electrode with H2SO4 and H2SO4-KI as an electrolyte. The electrochemical performances of fabricated supercapacitors were investigated by impedance spectroscopy, cyclic voltammetry and charge-discharge techniques. The maximum capacitance ` C' was observed with redox additives-based electrolyte system comprising 1 M H2SO4-0.3 M KI (1072 F g- 1), which is very much higher than conventional 1 M H2SO4 (61.3 F g- 1) aqueous electrolyte-based ultracapacitors. It corresponds to an energy density of 20.49 Wh kg- 1 at 2.1 A g- 1 for redox additive-based electrolyte, which is six times higher as compared to that of pristine electrolyte (1 M H2SO4) having energy density of only 3.36 Wh kg- 1. The temperature dependence behavior of fabricated cell was also analyzed, which shows increasing pattern in its capacitance values in a temperature range of 5-70 °C. Under cyclic stability test, redox electrolyte-based system shows almost 100% capacitance retention up to 5000 cycles and even more. For comparison, ultracapacitors based on polymer gel electrolyte polyvinyl alcohol (PVA) (10 wt%)—{H2SO4 (1 M)-KI (0.3 M)} (90 wt%) have been fabricated and characterized with the same electrode materials.

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

Titanium nitride as an electrocatalyst for V(II)/V(III) redox couples in all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Yang, Chunmei; Wang, Haining; Lu, Shanfu; Wu, Chunxiao; Liu, Yiyang; Tan, Qinglong; Liang, Dawei; Xiang, Yan

2015-01-01

Titanium nitride nanoparticles (TiN NPs) are proposed as a novel catalyst towards the V(II)/V(III) redox pair for the negative electrode in vanadium redox flow batteries (VRFB). Electrochemical properties of TiN NPs were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that TiN NPs demonstrate better electrochemical activity and reversibility for the processes of V(II)/V(III) redox couples as compared with the graphite NPs. TiN NPs facilitate the charge transfer in the V(II)/V(III) redox reaction. Performance of a VRFB using a TiN NPs coated carbon paper as a negative electrode is much higher than that of a VRFB with a raw carbon paper electrode. The columbic efficiency (CE), the voltage efficiency (VE) and the energy efficiency (EE) of the VRFB single cell at charge-discharge current density of 30 mA/cm 2 are 91.74%, 89.11% and 81.74%, respectively. During a 50 charge-discharge cycles test, the CE values of VRFB with TiN NPs consistently remain higher than 90%.

A bulk micromachined lead zinconate titanate cantilever energy harvester with inter-digital IrO(x) electrodes.

Science.gov (United States)

Park, Jongcheol; Park, Jae Yeong

2013-10-01

A piezoelectric vibration energy harvester with inter-digital IrO(x) electrode was developed by using silicon bulk micromachining technology. Most PZT cantilever based energy harvesters have utilized platinum electrode material. However, the PZT fatigue characteristics and adhesion/delamination problems caused by the platinum electrode might be serious problem in reliability of energy harvester. To address these problems, the iridium oxide was newly applied. The proposed energy harvester was comprised of bulk micromachined silicon cantilever with 800 x 1000 x 20 microm3, which having a silicon supporting membrane, sol-gel-spin coated Pb(Zr52, Ti48)O3 thin film, and sputtered inter-digitally shaped IrO(x) electrodes, and silicon inertial mass with 1000 x 1000 x 500 microm3 to adjust its resonant frequency. The fabricated energy harvester generated 1 microW of electrical power to 470 komega of load resistance and 1.4 V(peak-to-peak) from a vibration of 0.4 g at 1.475 kHz. The corresponding power density was 6.25 mW x cm(-3) x g(-2). As expected, its electrical failure was significantly improved.

Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts.

Science.gov (United States)

Yuan, Zhe; Peng, Hong-Jie; Hou, Ting-Zheng; Huang, Jia-Qi; Chen, Cheng-Meng; Wang, Dai-Wei; Cheng, Xin-Bing; Wei, Fei; Zhang, Qiang

2016-01-13

Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

Characterization of the polymer energy landscape in polymer:fullerene bulk heterojunctions with pure and mixed phases

KAUST Repository

Sweetnam, Sean

2014-10-08

Theoretical and experimental studies suggest that energetic offsets between the charge transport energy levels in different morphological phases of polymer:fullerene bulk heterojunctions may improve charge separation and reduce recombination in polymer solar cells (PSCs). In this work, we use cyclic voltammetry, UV-vis absorption, and ultraviolet photoelectron spectroscopy to characterize hole energy levels in the polymer phases of polymer:fullerene bulk heterojunctions. We observe an energetic offset of up to 150 meV between amorphous and crystalline polymer due to bandgap widening associated primarily with changes in polymer conjugation length. We also observe an energetic offset of up to 350 meV associated with polymer:fullerene intermolecular interactions. The first effect has been widely observed, but the second effect is not always considered despite being larger in magnitude for some systems. These energy level shifts may play a major role in PSC performance and must be thoroughly characterized for a complete understanding of PSC function.

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.

Exercise and Glycemic Control: Focus on Redox Homeostasis and Redox-Sensitive Protein Signaling

Science.gov (United States)

Parker, Lewan; Shaw, Christopher S.; Stepto, Nigel K.; Levinger, Itamar

2017-01-01

Physical inactivity, excess energy consumption, and obesity are associated with elevated systemic oxidative stress and the sustained activation of redox-sensitive stress-activated protein kinase (SAPK) and mitogen-activated protein kinase signaling pathways. Sustained SAPK activation leads to aberrant insulin signaling, impaired glycemic control, and the development and progression of cardiometabolic disease. Paradoxically, acute exercise transiently increases oxidative stress and SAPK signaling, yet postexercise glycemic control and skeletal muscle function are enhanced. Furthermore, regular exercise leads to the upregulation of antioxidant defense, which likely assists in the mitigation of chronic oxidative stress-associated disease. In this review, we explore the complex spatiotemporal interplay between exercise, oxidative stress, and glycemic control, and highlight exercise-induced reactive oxygen species and redox-sensitive protein signaling as important regulators of glucose homeostasis. PMID:28529499

STAT3-RXR-Nrf2 activates systemic redox and energy homeostasis upon steep decline in pO2 gradient.

Science.gov (United States)

Paul, Subhojit; Gangwar, Anamika; Bhargava, Kalpana; Ahmad, Yasmin

2018-04-01

Hypobaric hypoxia elicits several patho-physiological manifestations, some of which are known to be lethal. Among various molecular mechanisms proposed so far, perturbation in redox state due to imbalance between radical generation and antioxidant defence is promising. These molecular events are also related to hypoxic status of cancer cells and therefore its understanding has extended clinical advantage beyond high altitude hypoxia. In present study, however, the focus was to understand and propose a model for rapid acclimatization of high altitude visitors to enhance their performance based on molecular changes. We considered using simulated hypobaric hypoxia at some established thresholds of high altitude stratification based on known physiological effects. Previous studies have focused on the temporal aspect while overlooking the effects of varying pO 2 levels during exposure to hypobaric hypoxia. The pO 2 levels, indicative of altitude, are crucial to redox homeostasis and can be the limiting factor during acclimatization to hypobaric hypoxia. In this study we present the effects of acute (24h) exposure to high (3049m; pO 2 : 71kPa), very high (4573m; pO 2 : 59kPa) and extreme altitude (7620m; pO 2 : 40kPa) zones on lung and plasma using semi-quantitative redox specific transcripts and quantitative proteo-bioinformatics workflow in conjunction with redox stress assays. It was observed that direct exposure to extreme altitude caused 100% mortality, which turned into high survival rate after pre-exposure to 59kPa, for which molecular explanation were also found. The pO 2 of 59kPa (very high altitude zone) elicits systemic energy and redox homeostatic processes by modulating the STAT3-RXR-Nrf2 trio. Finally we posit the various processes downstream of STAT3-RXR-Nrf2 and the plasma proteins that can be used to ascertain the redox status of an individual. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Estimation of track registration efficiency in solution medium and study of gamma irradiation effects on the bulk-etch rate and the activation energy for bulk etching of CR-39 (DOP) Solid State Nuclear Track Detector

International Nuclear Information System (INIS)

Kalsi, P.C.

2010-01-01

The fission track registration efficiency of diethylene glycol bis allyl carbonate (dioctyl phthalate doped) (CR-39 (DOP)) solid state nuclear track detector (SSNTD) in solution medium (K wet ) has been experimentally determined and is found to be (9.7 ± 0.5).10 -4 cm. This is in good agreement with the values of other SSNTDs. The gamma irradiation effects in the dose range of 50.0-220.0 kGy on the bulk etch rate, V b and the activation energy for bulk etching, E of this solid state nuclear track detector (SSNTD) have also been studied. It is observed that the bulk etch rates increase and the activation energies for bulk etching decrease with the increase in gamma dose. These results have been explained on the basis of scission of the detector due to gamma irradiation

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

Study to establish cost predictions for the production of Redox chemicals

Science.gov (United States)

Ammann, P. R.; Loreth, M.; Harvey, W. W.

1982-01-01

The chromium and iron chloride chemicals are significant first costs for NASA Redox energy storage systems. This study was performed to determine the lowest cost at which chromium and iron chlorides could be obtained for a complex of redox energy storage systems. In addition, since the solutions gradually become intermixed during the course of operation of Redox units, it was an objective to evaluate schemes for regeneration of the operating solutions. Three processes were evaluated for the production of chromium and iron chlorides. As a basis for the preliminary plant design and economic evaluation, it was assumed that the plant would produce about 25,000 tons of contained chromium as CrCl3 and an equivalent molar quantity of FeCl2. Preliminary plant designs, including materials and energy balances and sizing of major equipment, were prepared, and capital and operating costs were estimated.

Redox-Active Star Molecules Incorporating the 4-Benzoylpyridinium Cation - Implications for the Charge Transfer Along Branches vs. Across the Perimeter in Dendrimer

Science.gov (United States)

Leventis, Nicholas; Yang, Jinua; Fabrizio,Even F.; Rawashdeh, Abdel-Monem M.; Oh, Woon Su; Sotiriou-Leventis, Chariklia

2004-01-01

Dendrimers are self-repeating globular branched star molecules, whose fractal structure continues to fascinate, challenge, and inspire. Functional dendrimers may incorporate redox centers, and potential applications include antennae molecules for light harvesting, sensors, mediators, and artificial biomolecules. We report the synthesis and redox properties of four star systems incorporating the 4-benzoyl-N-alkylpyridinium cation; the redox potential varies along the branches but remains constant at fixed radii. Bulk electrolysis shows that at a semi-infinite time scale all redox centers are electrochemically accessible. However, voltammetric analysis (cyclic voltammetry and differential pulse voltammetry) shows that on1y two of the three redox-active centers in the perimeter are electrochemically accessible during potential sweeps as slow as 20 mV/s and as fast as 10 V/s. On the contrary, both redox centers along branches are accessible electrochemically within the same time frame. These results are explained in terms of slow through-space charge transfer and the globular 3-D folding of the molecules and are discussed in terms of their implications on the design of efficient redox functional dendrimers.

Extending roGFP Emission via Förster-Type Resonance Energy Transfer Relay Enables Simultaneous Dual Compartment Ratiometric Redox Imaging in Live Cells.

Science.gov (United States)

Norcross, Stevie; Trull, Keelan J; Snaider, Jordan; Doan, Sara; Tat, Kiet; Huang, Libai; Tantama, Mathew

2017-11-22

Reactive oxygen species (ROS) mediate both intercellular and intraorganellar signaling, and ROS propagate oxidative stress between cellular compartments such as mitochondria and the cytosol. Each cellular compartment contains its own sources of ROS as well as antioxidant mechanisms, which contribute to dynamic fluctuations in ROS levels that occur during signaling, metabolism, and stress. However, the coupling of redox dynamics between cellular compartments has not been well studied because of the lack of available sensors to simultaneously measure more than one subcellular compartment in the same cell. Currently, the redox-sensitive green fluorescent protein, roGFP, has been used extensively to study compartment-specific redox dynamics because it provides a quantitative ratiometric readout and it is amenable to subcellular targeting as a genetically encoded sensor. Here, we report a new family of genetically encoded fluorescent protein sensors that extend the fluorescence emission of roGFP via Förster-type resonance energy transfer to an acceptor red fluorescent protein for dual-color live-cell microscopy. We characterize the redox and optical properties of the sensor proteins, and we demonstrate that they can be used to simultaneously measure cytosolic and mitochondrial ROS in living cells. Furthermore, we use these sensors to reveal cell-to-cell heterogeneity in redox coupling between the cytosol and mitochondria when neuroblastoma cells are exposed to reductive and metabolic stresses.

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

2016-01-01

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. PMID:27966605

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.

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.

Bulk superconducting gap of V{sub 3}Si studied by low-energy ultrahigh-resolution photoemission spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Sato, T., E-mail: t-sato@arpes.phys.tohoku.ac.jp [Department of Physics, Tohoku University, Sendai 980-8578 (Japan); Souma, S. [WPI Research Center, Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Nakayama, K. [Department of Physics, Tohoku University, Sendai 980-8578 (Japan); Sugawara, K. [WPI Research Center, Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Toyota, N. [Department of Physics, Tohoku University, Sendai 980-8578 (Japan); Takahashi, T. [Department of Physics, Tohoku University, Sendai 980-8578 (Japan); WPI Research Center, Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)

2016-04-15

Highlights: • We report ultrahigh-resolution photoemission spectroscopy of A15 compound V{sub 3}Si. • We found a sharp quasiparticle peak due to superconducting-gap opening. • The surface metallic component is negligibly small in the bulk-sensitive measurement. • We show that V{sub 3}Si is a single-gap s-wave superconductor. - Abstract: We have performed low-energy ultrahigh-resolution photoemission spectroscopy (PES) of A15 compound V{sub 3}Si with a xenon-plasma discharge lamp to elucidate the bulk superconducting gap. Below the superconducting transition temperature (T{sub c} = 15.9 K), we found a sharp quasiparticle peak at the Fermi level in the PES spectrum. The gap spectrum is well fitted by a single s-wave superconducting-gap function together with a dip structure at ∼30 meV suggestive of a strong electron-phonon coupling. The anomalous in-gap state previously observed in the PES measurement with high-energy photons is absent or negligibly small in the present bulk-sensitive measurement. The present PES result shows that V{sub 3}Si is a single-gap s-wave superconductor.

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

OpenAIRE

Kristina Wedege; Emil Dražević; Denes Konya; Anders Bentien

2016-01-01

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 ...

Redox proteomics of tomato in response to Pseudomonas syringae infection

Science.gov (United States)

Balmant, Kelly Mayrink; Parker, Jennifer; Yoo, Mi-Jeong; Zhu, Ning; Dufresne, Craig; Chen, Sixue

2015-01-01

Unlike mammals with adaptive immunity, plants rely on their innate immunity based on pattern-triggered immunity (PTI) and effector-triggered immunity (ETI) for pathogen defense. Reactive oxygen species, known to play crucial roles in PTI and ETI, can perturb cellular redox homeostasis and lead to changes of redox-sensitive proteins through modification of cysteine sulfhydryl groups. Although redox regulation of protein functions has emerged as an important mechanism in several biological processes, little is known about redox proteins and how they function in PTI and ETI. In this study, cysTMT proteomics technology was used to identify similarities and differences of protein redox modifications in tomato resistant (PtoR) and susceptible (prf3) genotypes in response to Pseudomonas syringae pv tomato (Pst) infection. In addition, the results of the redox changes were compared and corrected with the protein level changes. A total of 90 potential redox-regulated proteins were identified with functions in carbohydrate and energy metabolism, biosynthesis of cysteine, sucrose and brassinosteroid, cell wall biogenesis, polysaccharide/starch biosynthesis, cuticle development, lipid metabolism, proteolysis, tricarboxylic acid cycle, protein targeting to vacuole, and oxidation–reduction. This inventory of previously unknown protein redox switches in tomato pathogen defense lays a foundation for future research toward understanding the biological significance of protein redox modifications in plant defense responses. PMID:26504582

High energy density redox flow device

Science.gov (United States)

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

2014-05-13

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.

T-REX on-demand redox targeting in live cells.

Science.gov (United States)

Parvez, Saba; Long, Marcus J C; Lin, Hong-Yu; Zhao, Yi; Haegele, Joseph A; Pham, Vanha N; Lee, Dustin K; Aye, Yimon

2016-12-01

This protocol describes targetable reactive electrophiles and oxidants (T-REX)-a live-cell-based tool designed to (i) interrogate the consequences of specific and time-resolved redox events, and (ii) screen for bona fide redox-sensor targets. A small-molecule toolset comprising photocaged precursors to specific reactive redox signals is constructed such that these inert precursors specifically and irreversibly tag any HaloTag-fused protein of interest (POI) in mammalian and Escherichia coli cells. Syntheses of the alkyne-functionalized endogenous reactive signal 4-hydroxynonenal (HNE(alkyne)) and the HaloTag-targetable photocaged precursor to HNE(alkyne) (also known as Ht-PreHNE or HtPHA) are described. Low-energy light prompts photo-uncaging (t 1/2 <1-2 min) and target-specific modification. The targeted modification of the POI enables precisely timed and spatially controlled redox events with no off-target modification. Two independent pathways are described, along with a simple setup to functionally validate known targets or discover novel sensors. T-REX sidesteps mixed responses caused by uncontrolled whole-cell swamping with reactive signals. Modification and downstream response can be analyzed by in-gel fluorescence, proteomics, qRT-PCR, immunofluorescence, fluorescence resonance energy transfer (FRET)-based and dual-luciferase reporters, or flow cytometry assays. T-REX targeting takes 4 h from initial probe treatment. Analysis of targeted redox responses takes an additional 4-24 h, depending on the nature of the pathway and the type of readouts used.

Metabolic Control of Redox and Redox Control of Metabolism in Plants

Science.gov (United States)

Fernie, Alisdair R.

2014-01-01

Abstract Significance: Reduction-oxidation (Redox) status operates as a major integrator of subcellular and extracellular metabolism and is simultaneously itself regulated by metabolic processes. Redox status not only dominates cellular metabolism due to the prominence of NAD(H) and NADP(H) couples in myriad metabolic reactions but also acts as an effective signal that informs the cell of the prevailing environmental conditions. After relay of this information, the cell is able to appropriately respond via a range of mechanisms, including directly affecting cellular functioning and reprogramming nuclear gene expression. Recent Advances: The facile accession of Arabidopsis knockout mutants alongside the adoption of broad-scale post-genomic approaches, which are able to provide transcriptomic-, proteomic-, and metabolomic-level information alongside traditional biochemical and emerging cell biological techniques, has dramatically advanced our understanding of redox status control. This review summarizes redox status control of metabolism and the metabolic control of redox status at both cellular and subcellular levels. Critical Issues: It is becoming apparent that plastid, mitochondria, and peroxisome functions influence a wide range of processes outside of the organelles themselves. While knowledge of the network of metabolic pathways and their intraorganellar redox status regulation has increased in the last years, little is known about the interorganellar redox signals coordinating these networks. A current challenge is, therefore, synthesizing our knowledge and planning experiments that tackle redox status regulation at both inter- and intracellular levels. Future Directions: Emerging tools are enabling ever-increasing spatiotemporal resolution of metabolism and imaging of redox status components. Broader application of these tools will likely greatly enhance our understanding of the interplay of redox status and metabolism as well as elucidating and

Impedance aspect of charge storage at graphite and glassy carbon electrodes in potassium hexacyanoferrate (II redox active electrolyte

Directory of Open Access Journals (Sweden)

Katja Magdić

2016-04-01

Full Text Available Different types of charge storage mechanisms at unmodified graphite vs. glassy carbon electrodes in acid sulphate supporting solution containing potassium hexacyanoferrate (II redox active electrolyte, have been revealed by electrochemical impedance spectroscopy and supported by cyclic voltammetry experiments. Reversible charge transfer of Fe(CN63-/4- redox reaction detected by assessment of CVs of glassy carbon electrode, is in impedance spectra indicated by presence of bulk diffusion impedance and constant double-layer/pseudocapacitive electrode impedance compared to that measured in the pure supporting electrolyte. Some surface retention of redox species detected by assessment of CVs of graphite electrode is in impedance spectra indicated by diffusion impedance coupled in this case by diminishing of double-layer/pseudo­capacitive impedance compared to that measured in the pure supporting electrolyte. This phenomenon is ascribed to contribution of additional pseudocapacitive impedance generated by redox reaction of species confined at the electrode surface.

Evaluation of bulk and surfaces absorption edge energy of sol-gel-dip-coating SnO2 thin films

Directory of Open Access Journals (Sweden)

Emerson Aparecido Floriano

2010-12-01

Full Text Available The absorption edge and the bandgap transition of sol-gel-dip-coating SnO2 thin films, deposited on quartz substrates, are evaluated from optical absorption data and temperature dependent photoconductivity spectra. Structural properties of these films help the interpretation of bandgap transition nature, since the obtained nanosized dimensions of crystallites are determinant on dominant growth direction and, thus, absorption energy. Electronic properties of the bulk and (110 and (101 surfaces are also presented, calculated by means of density functional theory applied to periodic calculations at B3LYP hybrid functional level. Experimentally obtained absorption edge is compared to the calculated energy band diagrams of bulk and (110 and (101 surfaces. The overall calculated electronic properties in conjunction with structural and electro-optical experimental data suggest that the nature of the bandgap transition is related to a combined effect of bulk and (101 surface, which presents direct bandgap transition.

Extracting the redox orbitals in Li battery materials with high-resolution x-ray compton scattering spectroscopy.

Science.gov (United States)

Suzuki, K; Barbiellini, B; Orikasa, Y; Go, N; Sakurai, H; Kaprzyk, S; Itou, M; Yamamoto, K; Uchimoto, Y; Wang, Yung Jui; Hafiz, H; Bansil, A; Sakurai, Y

2015-02-27

We present an incisive spectroscopic technique for directly probing redox orbitals based on bulk electron momentum density measurements via high-resolution x-ray Compton scattering. Application of our method to spinel Li_{x}Mn_{2}O_{4}, a lithium ion battery cathode material, is discussed. The orbital involved in the lithium insertion and extraction process is shown to mainly be the oxygen 2p orbital. Moreover, the manganese 3d states are shown to experience spatial delocalization involving 0.16±0.05 electrons per Mn site during the battery operation. Our analysis provides a clear understanding of the fundamental redox process involved in the working of a lithium ion battery.

Solid-state electroanalytical characterization of the nonaqueous proton-conducting redox gel containing polyoxometallates

International Nuclear Information System (INIS)

Lewera, Adam; Zukowska, Grazyna; Miecznikowski, Krzysztof; Chojak, Malgorzata; Wieczorek, Wladyslaw; Kulesza, Pawel J.

2005-01-01

A novel polymetacrylate-based redox-conducting polymeric gel, into which Keggin-type polyoxometallate, phosphododecatungstic acid (H 3 PW 12 O 40 ), had been incorporated, was electrochemically characterized in the absence of external liquid supporting electrolyte using an ultramicrodisk-working electrode. The phosphotungstate component (15 wt.% of the gel block) was entrapped as the polar organic solvent solution within pores of the polymer matrix. H 3 PW 12 O 40 plays bifunctional role: it provides well-behaved redox centers and serves as strong acid (source of mobile protons). The solid-state voltammetric properties of the system are defined by the reversible one-electron transfers between phosphotungstate redox centers. The following parameters have been determined from the combination of potential step experiments performed in two limiting (radial and linear) diffusional regimes: the concentration of heteropolytungstate redox centers, 6 x 10 -2 mol dm -3 , and the apparent diffusion coefficient, 5 x 10 -7 cm 2 s -1 . The room temperature ionic (protonic) conductivity of the bulk gel was equal to 1.6 x 10 -3 S cm -1 . The charge propagation mechanism was found to be primarily controlled by physical diffusion of heteropolytungstate units within the gel pores rather than by electron hopping (self-exchange) between mixed-valence sites

Tunnelling determined superconducting energy gap of bulk single crystal aluminum

International Nuclear Information System (INIS)

Civiak, R.L.

1974-01-01

A procedure has been developed for fabricating Giaver tunnel junctions on bulk aluminum. Al-I-Ag junctions were prepared, where I is the naturally formed oxide on the polished, chemically treated aluminum surface. The aluminum energy gap was determined from tunneling conductance curves obtained from samples oriented in three different crystal directions, and as a function of magnetic field in each of these orientations. In contrast to the results of microwave absorption measurements on superconducting aluminum, no magnetic field dependence could be measured for either the average gap or the spread in gap values of the tunneling electrons. This is consistent with commonly accepted tunneling selection rules, and Garfunkel's interpretation of the microwave behavior which depended upon adjusting the energy spectrum of only the electrons traveling parallel to the surface in the presence of a magnetic field. The energy gaps measured for samples oriented in the 100, 110 and 111 directions are 3.52, 3.50 and 3.39 kT/sub c/, respectively. The trend in the anisotropy is the same as in the calculation of Leavens and Carbotte, however, the magnitude of the anisotropy is smaller than in their calculation and that which previous measurements have indicated

The role of nanomaterials in redox-based supercapacitors for next generation energy storage devices

Science.gov (United States)

Zhao, Xin; Sánchez, Beatriz Mendoza; Dobson, Peter J.; Grant, Patrick S.

2011-03-01

The development of more efficient electrical storage is a pressing requirement to meet future societal and environmental needs. This demand for more sustainable, efficient energy storage has provoked a renewed scientific and commercial interest in advanced capacitor designs in which the suite of experimental techniques and ideas that comprise nanotechnology are playing a critical role. Capacitors can be charged and discharged quickly and are one of the primary building blocks of many types of electrical circuit, from microprocessors to large-sale power supplies, but usually have relatively low energy storage capability when compared with batteries. The application of nanostructured materials with bespoke morphologies and properties to electrochemical supercapacitors is being intensively studied in order to provide enhanced energy density without comprising their inherent high power density and excellent cyclability. In particular, electrode materials that exploit physical adsorption or redox reactions of electrolyte ions are foreseen to bridge the performance disparity between batteries with high energy density and capacitors with high power density. In this review, we present some of the novel nanomaterial systems applied for electrochemical supercapacitors and show how material morphology, chemistry and physical properties are being tailored to provide enhanced electrochemical supercapacitor performance.

Impacts of Variable Renewable Energy on Bulk Power System Assets, Pricing, and Costs

Energy Technology Data Exchange (ETDEWEB)

Wiser, Ryan H. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Mills, Andrew [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Seel, Joachim [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Levin, Todd [Argonne National Lab. (ANL), Argonne, IL (United States); Botterud, Audun [Argonne National Lab. (ANL), Argonne, IL (United States)

2017-11-29

We synthesize available literature, data, and analysis on the degree to which growth in variable renewable energy (VRE) has impacted to date or might in the future impact bulk power system assets, pricing, and costs. We do not analyze impacts on specific power plants, instead focusing on national and regional system-level trends. The issues addressed are highly context dependent—affected by the underlying generation mix of the system, the amount of wind and solar penetration, and the design and structure of the bulk power system in each region. Moreover, analyzing the impacts of VRE on the bulk power system is a complex area of research and there is much more to be done to increase understanding of how VRE impacts the dynamics of current and future electricity markets. While more analysis is warranted, including additional location-specific assessments, several high-level findings emerge from this synthesis: -VRE Is Already Impacting the Bulk Power Market -VRE Impacts on Average Wholesale Prices Have Been Modest -VRE Impacts on Power Plant Retirements Have So Far Been Limited -VRE Impacts on the Bulk Power Market will Grow with Penetration -The ’System Value’ of VRE will Decline with Penetration -Power System Flexibility Can Reduce the Rate of VRE Value Decline All generation types are unique in some respect—bringing benefits and challenges to the power system—and wholesale markets, industry investments, and operational procedures have evolved over time to manage the characteristics of a changing generation fleet. With increased VRE penetrations, power system planners, operators, regulators, and policymakers will continue to be challenged to develop methods to smoothly and cost-effectively manage the reliable integration of these new and growing sources of electricity supply.

Conductance and bulk vertical detachment energy of hydrated sulphate and oxalate dianions: a theoretical study

Science.gov (United States)

Pathak, Arup Kumar

2014-06-01

Analytical expressions have been derived for the vertical detachment energy (VDE) for hydrated sulphate (SO2 -4) and oxalate (C2O2 -4) dianions that can be used to calculate the same over a wide range of cluster sizes including the bulk from the knowledge of VDE for a finite number of stable clusters. The calculated bulk detachment energies are found to be very good in agreement (within 5%) with the available experimental results for both the systems. It is observed that two or more water molecules will be essential for the stability of sulphate and oxalate dianions against spontaneous electron loss and this is consistent with the experiment. We have, for the first time, provided a scheme to calculate the radius of the solvent berg for sulphate and oxalate dianions. The calculated conductivity values for the sulphate and oxalate dianions using Stokes-Einstein relation and the radius of solvent berg are found to be very good in agreement (within 4%) with the available experimental results.

Back-reactions, short-circuits, leaks and other energy wasteful reactions in biological electron transfer: redox tuning to survive life in O(2).

Science.gov (United States)

Rutherford, A William; Osyczka, Artur; Rappaport, Fabrice

2012-03-09

The energy-converting redox enzymes perform productive reactions efficiently despite the involvement of high energy intermediates in their catalytic cycles. This is achieved by kinetic control: with forward reactions being faster than competing, energy-wasteful reactions. This requires appropriate cofactor spacing, driving forces and reorganizational energies. These features evolved in ancestral enzymes in a low O(2) environment. When O(2) appeared, energy-converting enzymes had to deal with its troublesome chemistry. Various protective mechanisms duly evolved that are not directly related to the enzymes' principal redox roles. These protective mechanisms involve fine-tuning of reduction potentials, switching of pathways and the use of short circuits, back-reactions and side-paths, all of which compromise efficiency. This energetic loss is worth it since it minimises damage from reactive derivatives of O(2) and thus gives the organism a better chance of survival. We examine photosynthetic reaction centres, bc(1) and b(6)f complexes from this view point. In particular, the evolution of the heterodimeric PSI from its homodimeric ancestors is explained as providing a protective back-reaction pathway. This "sacrifice-of-efficiency-for-protection" concept should be generally applicable to bioenergetic enzymes in aerobic environments. Copyright © 2012 Federation of European Biochemical Societies. All rights reserved.

Ultrathin Hierarchical Porous Carbon Nanosheets for High-Performance Supercapacitors and Redox Electrolyte Energy Storage.

Science.gov (United States)

Jayaramulu, Kolleboyina; Dubal, Deepak P; Nagar, Bhawna; Ranc, Vaclav; Tomanec, Ondrej; Petr, Martin; Datta, Kasibhatta Kumara Ramanatha; Zboril, Radek; Gómez-Romero, Pedro; Fischer, Roland A

2018-04-01

The design of advanced high-energy-density supercapacitors requires the design of unique materials that combine hierarchical nanoporous structures with high surface area to facilitate ion transport and excellent electrolyte permeability. Here, shape-controlled 2D nanoporous carbon sheets (NPSs) with graphitic wall structure through the pyrolysis of metal-organic frameworks (MOFs) are developed. As a proof-of-concept application, the obtained NPSs are used as the electrode material for a supercapacitor. The carbon-sheet-based symmetric cell shows an ultrahigh Brunauer-Emmett-Teller (BET)-area-normalized capacitance of 21.4 µF cm -2 (233 F g -1 ), exceeding other carbon-based supercapacitors. The addition of potassium iodide as redox-active species in a sulfuric acid (supporting electrolyte) leads to the ground-breaking enhancement in the energy density up to 90 Wh kg -1 , which is higher than commercial aqueous rechargeable batteries, maintaining its superior power density. Thus, the new material provides a double profits strategy such as battery-level energy and capacitor-level power density. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amplified and in situ detection of redox-active metabolite using a biobased redox capacitor.

Science.gov (United States)

Kim, Eunkyoung; Gordonov, Tanya; Bentley, William E; Payne, Gregory F

2013-02-19

Redox cycling provides a mechanism to amplify electrochemical signals for analyte detection. Previous studies have shown that diverse mediators/shuttles can engage in redox-cycling reactions with a biobased redox capacitor that is fabricated by grafting redox-active catechols onto a chitosan film. Here, we report that redox cycling with this catechol-chitosan redox capacitor can amplify electrochemical signals for detecting a redox-active bacterial metabolite. Specifically, we studied the redox-active bacterial metabolite pyocyanin that is reported to be a virulence factor and signaling molecule for the opportunistic pathogen P. aeruginosa. We demonstrate that redox cycling can amplify outputs from various electrochemical methods (cyclic voltammetry, chronocoulometry, and differential pulse voltammetry) and can lower the detection limit of pyocyanin to 50 nM. Further, the compatibility of this biobased redox capacitor allows the in situ monitoring of the production of redox-active metabolites (e.g., pyocyanin) during the course of P. aeruginosa cultivation. We anticipate that the amplified output of redox-active virulence factors should permit an earlier detection of life-threatening infections by the opportunistic pathogen P. aeruginosa while the "bio-compatibility" of this measurement approach should facilitate in situ study of the spatiotemporal dynamics of bacterial redox signaling.

Functionalized carbon nanotube based hybrid electrochemical capacitors using neutral bromide redox-active electrolyte for enhancing energy density

Science.gov (United States)

Tang, Xiaohui; Lui, Yu Hui; Chen, Bolin; Hu, Shan

2017-06-01

A hybrid electrochemical capacitor (EC) with enhanced energy density is realized by integrating functionalized carbon nanotube (FCNT) electrodes with redox-active electrolyte that has a neutral pH value (1 M Na2SO4 and 0.5 M KBr mixed aqueous solution). The negative electrode shows an electric double layer capacitor-type behavior. On the positive electrode, highly reversible Br-/Br3- redox reactions take place, presenting a battery-type behavior, which contributes to increase the capacitance of the hybrid cell. The voltage window of the whole cell is extended up to 1.5 V because of the high over-potentials of oxygen and hydrogen evolution reactions in the neutral electrolyte. Compared with raw CNT, the FCNT has better wettability in the aqueous electrolyte and contributes to increase the electric double layer capacitance of the cell. As a result, the maximum energy density of 28.3 Wh kg-1 is obtained from the hybrid EC at 0.5 A g-1 without sacrificing its power density, which is around 4 times larger than that of the electrical double layer capacitor constructed by FCNT electrodes and 1 M Na2SO4 electrolyte. Moreover, the discharge capacity retained 86.3% of its initial performance after 10000 cycles of galvanostatic charge and discharge test (10 A/g), suggesting its long life cycle even at high current loading.

Impacts of shallow geothermal energy production on redox processes and microbial communities.

Science.gov (United States)

Bonte, Matthijs; Röling, Wilfred F M; Zaura, Egija; van der Wielen, Paul W J J; Stuyfzand, Pieter J; van Breukelen, Boris M

2013-12-17

Shallow geothermal systems are increasingly being used to store or harvest thermal energy for heating or cooling purposes. This technology causes temperature perturbations exceeding the natural variations in aquifers, which may impact groundwater quality. Here, we report the results of laboratory experiments on the effect of temperature variations (5-80 °C) on redox processes and associated microbial communities in anoxic unconsolidated subsurface sediments. Both hydrochemical and microbiological data showed that a temperature increase from 11 °C (in situ) to 25 °C caused a shift from iron-reducing to sulfate-reducing and methanogenic conditions. Bioenergetic calculations could explain this shift. A further temperature increase (>45 °C) resulted in the emergence of a thermophilic microbial community specialized in fermentation and sulfate reduction. Two distinct maxima in sulfate reduction rates, of similar orders of magnitude (5 × 10(-10) M s(-1)), were observed at 40 and 70 °C. Thermophilic sulfate reduction, however, had a higher activation energy (100-160 kJ mol(-1)) than mesophilic sulfate reduction (30-60 kJ mol(-1)), which might be due to a trade-off between enzyme stability and activity with thermostable enzymes being less efficient catalysts that require higher activation energies. These results reveal that while sulfate-reducing functionality can withstand a substantial temperature rise, other key biochemical processes appear more temperature sensitive.

Attenuation of bulk organic matter, nutrients (N and P), and pathogen indicators during soil passage: Effect of temperature and redox conditions in simulated soil aquifer treatment (SAT)

KAUST Repository

Abel, Chol D T

2012-07-22

Soil aquifer treatment (SAT) is a costeffective natural wastewater treatment and reuse technology. It is an environmentally friendly technology that does not require chemical usage and is applicable to both developing and developed countries. However, the presence of organic matter, nutrients, and pathogens poses a major health threat to the population exposed to partially treated wastewater or reclaimed water through SAT. Laboratory-based soil column and batch experiments simulating SAT were conducted to examine the influence of temperature variation and oxidation-reduction (redox) conditions on removal of bulk organic matter, nutrients, and indicator microorganisms using primary effluent. While an average dissolved organic carbon (DOC) removal of 17.7 % was achieved in soil columns at 5 °C, removal at higher temperatures increased by 10 % increments with increase in temperature by 5 °C over the range of 15 to 25 °C. Furthermore, soil column and batch experiments conducted under different redox conditions revealed higher DOC removal in aerobic (oxic) experiments compared to anoxic experiments. Aerobic soil columns exhibited DOC removal 15 % higher than that achieved in the anoxic columns, while aerobic batch showed DOC removal 7.8 % higher than the corresponding anoxic batch experiments. Ammonium-nitrogen removal greater than 99 % was observed at 20 and 25 °C, while 89.7 % was removed at 15 °C, but the removal substantially decreased to 8.8 % at 5 °C. While ammonium-nitrogen was attenuated by 99.9 % in aerobic batch reactors carried out at room temperature, anoxic experiments under similar conditions revealed 12.1 % ammonium-nitrogen reduction, corresponding to increase in nitrate-nitrogen and decrease in sulfate concentration. © Springer Science+Business Media B.V. 2012.

An FeIII Azamacrocyclic Complex as a pH-Tunable Catholyte and Anolyte for Redox-Flow Battery Applications.

Science.gov (United States)

Tsitovich, Pavel B; Kosswattaarachchi, Anjula M; Crawley, Matthew R; Tittiris, Timothy Y; Cook, Timothy R; Morrow, Janet R

2017-11-02

A reversible Fe 3+ /Fe 2+ redox couple of an azamacrocyclic complex is evaluated as an electrolyte with a pH-tunable potential range for aqueous redox-flow batteries (RFBs). The Fe III complex is formed by 1,4,7-triazacyclononane (TACN) appended with three 2-methyl-imidazole donors, denoted as Fe(Tim). This complex exhibits pH-sensitive redox couples that span E 1/2 (Fe 3+ /Fe 2+ )=317 to -270 mV vs. NHE at pH 3.3 and pH 12.8, respectively. The 590 mV shift in potential and kinetic inertness are driven by ionization of the imidazoles at various pH values. The Fe 3+ /Fe 2+ redox is proton-coupled at alkaline conditions, and bulk electrolysis is non-destructive. The electrolyte demonstrates high charge/discharge capacities at both acidic and alkaline conditions throughout 100 cycles. Given its tunable redox, fast electrochemical kinetics, exceptional stability/cyclability, this complex is promising for the design of aqueous RFB catholytes and anolytes that utilize the earth-abundant element iron. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

Science.gov (United States)

Abrams , Robert H.; Loague, Keith; Kent, Douglas B.

1998-01-01

The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

Cascade redox flow battery systems

Science.gov (United States)

Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

2014-07-22

A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

The Redox Proteome*

Science.gov (United States)

Go, Young-Mi; Jones, Dean P.

2013-01-01

The redox proteome consists of reversible and irreversible covalent modifications that link redox metabolism to biologic structure and function. These modifications, especially of Cys, function at the molecular level in protein folding and maturation, catalytic activity, signaling, and macromolecular interactions and at the macroscopic level in control of secretion and cell shape. Interaction of the redox proteome with redox-active chemicals is central to macromolecular structure, regulation, and signaling during the life cycle and has a central role in the tolerance and adaptability to diet and environmental challenges. PMID:23861437

Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration.

Science.gov (United States)

Birkner, Nancy; Navrotsky, Alexandra

2014-04-29

Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings.

Energy level alignment and sub-bandgap charge generation in polymer:fullerene bulk heterojunction solar cells.

Science.gov (United States)

Tsang, Sai-Wing; Chen, Song; So, Franky

2013-05-07

Using charge modulated electroabsorption spectroscopy (CMEAS), for the first time, the energy level alignment of a polymer:fullerene bulk heterojunction photovoltaic cell is directly measured. The charge-transfer excitons generated by the sub-bandgap optical pumping are coupled with the modulating electric field and introduce subtle changes in optical absorption in the sub-bandgap region. This minimum required energy for sub-bandgap charge genreation is defined as the effective bandgap. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A biomimetic redox flow battery based on flavin mononucleotide

OpenAIRE

Orita, A; Verde, MG; Sakai, M; Meng, YS

2016-01-01

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactio...

High-Energy Laser Interaction with Gases, Droplets, and Bulk Liquids.

Science.gov (United States)

Jarzembski, Maurice Anthony

Breakdown threshold intensities (I_ {rm TH}) were measured as functions of wavelengths and pressure for air, He, Ar, and Xe using a Nd:YAG pulsed laser. Multiphoton absorption dominates in the UV and cascade collision ionization dominates in the IR; however, both can be affected by other electron gain and loss processes. Presence of droplets lowers breakdown of gases due to field enhancements. Breakdown is initiated either in the droplet material or in the gas. At lambda = 0.532mum for a 50 μm dia. water droplet in He, Ar, and air for p pressure. For droplet -in-Xe, at p pressure. For droplet-in-Xe, at p 140 Torr, breakdown occurs outside the droplet and is dependent on gas pressure. Pressure dependence of breakdown was observed for 120mum dia. water droplets in Ar at p > 400 Torr. The required intensity for breakdown of droplet depends on I_{ rm TH} of bulk liquid and the effective field enhancement created by the droplet. The I _{rm TH} of droplet-in-air provides an upper limit to the propagation of a high energy laser beam in the atmosphere containing particles. By geometrical optics approach, a significant field enhancement located at the critical ring region, encircling the axis of the sphere in the forward direction at angle theta_{c}, was discovered where nonlinear processes can occur. This was confirmed experimentally and by Mie theory. Field enhancements calculated at the critical ring for water droplets of different sizes agree well with measurements. For a droplet of given size and real refractive index, the effective field enhancement and the volume over which it occurs are two important factors governing the occurrence of breakdown in droplets for both off resonance and on resonance conditions. Measurements of wavelength dependence of breakdown showed that in the UV, I_{rm TH} for droplets and bulk liquids were comparable and lower by few orders of magnitude from that of air. Transmittance and reflectance of bulk liquids in the UV change with

Redox flow batteries. Already an alternative storage solution for hybrid PV mini-grids?

Energy Technology Data Exchange (ETDEWEB)

Vetter, Matthias; Dennenmoser, Martin; Schwunk, Simon; Smolinka, Tom [Fraunhofer Institute for Solar Energy Systems (ISE), Freiburg (Germany); Doetsch, Christian; Berthold, Sascha [Fraunhofer Institute for Environmental, Safety and Energy Technology (UMSICHT), Oberhausen (Germany); Tuebke, Jens; Noack, Jens [Fraunhofer Institute for Chemical Technology (ICT), Karlsruhe (Germany)

2010-07-01

Due to the flexible scalability of the power to energy ratio redox flow batteries are a suitable solution for quite a lot of decentralized applications. E.g. the autonomy time of a stand-alone system or mini-grid can be raised by increasing the tank size of the redox flow battery. In this paper the test site ''Rappenecker Hof'' in the black forest is used as an example for simulation based life cycle cost analyses of a vanadium redox flow battery integrated in an autonomous hybrid PV system. Two cases with lead acid batteries are considered as benchmarks for economic viability of the redox flow battery solution in such applications. At the moment a 1 KW / 6 kWh system for decentralized solutions is developed and will be installed in the ''Solarhaus'' in Freiburg. The main results of the cell stack and system design as well as performance data are presented. Furthermore simulation models and the model based development of the ''Smart Redox flow Control'' are described. For the optimized integration of the storage unit in the energy system a communication interface for exchanging data with the supervisory energy management system is introduced. On this basis a SOC forecast according to a given demand profile can be determined. (orig.)

Solid-state electroanalytical characterization of the nonaqueous proton-conducting redox gel containing polyoxometallates

Energy Technology Data Exchange (ETDEWEB)

Lewera, Adam [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Zukowska, Grazyna [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warsaw (Poland); Miecznikowski, Krzysztof [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Chojak, Malgorzata [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland); Wieczorek, Wladyslaw [Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, PL-00-664 Warsaw (Poland); Kulesza, Pawel J. [Department of Chemistry, University of Warsaw, Pasteura 1, PL-02-093 Warsaw (Poland)]. E-mail: pkulesza@chem.uw.edu.pl

2005-04-22

A novel polymetacrylate-based redox-conducting polymeric gel, into which Keggin-type polyoxometallate, phosphododecatungstic acid (H{sub 3}PW{sub 12}O{sub 40}), had been incorporated, was electrochemically characterized in the absence of external liquid supporting electrolyte using an ultramicrodisk-working electrode. The phosphotungstate component (15 wt.% of the gel block) was entrapped as the polar organic solvent solution within pores of the polymer matrix. H{sub 3}PW{sub 12}O{sub 40} plays bifunctional role: it provides well-behaved redox centers and serves as strong acid (source of mobile protons). The solid-state voltammetric properties of the system are defined by the reversible one-electron transfers between phosphotungstate redox centers. The following parameters have been determined from the combination of potential step experiments performed in two limiting (radial and linear) diffusional regimes: the concentration of heteropolytungstate redox centers, 6 x 10{sup -2} mol dm{sup -3}, and the apparent diffusion coefficient, 5 x 10{sup -7} cm{sup 2} s{sup -1}. The room temperature ionic (protonic) conductivity of the bulk gel was equal to 1.6 x 10{sup -3} S cm{sup -1}. The charge propagation mechanism was found to be primarily controlled by physical diffusion of heteropolytungstate units within the gel pores rather than by electron hopping (self-exchange) between mixed-valence sites.

Energy consumption of chemical uranium enrichment

International Nuclear Information System (INIS)

Miyake, T.; Takeda, K.; Obanawa, H.

1987-01-01

A quantitative study of chemical separation energy for enriching uranium-235 by the redox chromatography was conducted. Isotope exchange reactions between U 4+ -UO 2 2+ ions in the enrichment column are maintained by the redox reactions. The chemical separation energy is ultimately supplied by hydrogen and oxygen gas for regenerating redox agents. The redox energy for the isotope separation is theoretically predicted as a function of the dynamic enrichment factor observed in the chromatographic development of uranium adsorption band. Thermodynamic treatments of the equilibrium reactions implies and inverse redox reaction which can be enhanced by the chemical potential of the ion-exchange reaction of oxidant. Experimental results showed 30 to 90% recovery of the redox energy by the inverse reaction. These results will devise a simplified redox chromatography process where a number of columns in one module is reduced

Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy

International Nuclear Information System (INIS)

Li, Qinghao; Chen, Jun; Chen, Yanxue; Yan, Shishen; Qiao, Ruimin; Zhuo, Zengqing; Hussain, Zahid; Yang, Wanli; Wray, L Andrew; Pan, Feng

2016-01-01

Most battery positive electrodes operate with a 3 d transition-metal (TM) reaction centre. A direct and quantitative probe of the TM states upon electrochemical cycling is valuable for understanding the detailed cycling mechanism and charge diffusion in the electrodes, which is related with many practical parameters of a battery. This review includes a comprehensive summary of our recent demonstrations of five different types of quantitative analysis of the TM states in battery electrodes based on soft x-ray absorption spectroscopy and multiplet calculations. In LiFePO 4 , a system of a well-known two-phase transformation type, the TM redox could be strictly determined through a simple linear combination of the two end-members. In Mn-based compounds, the Mn states could also be quantitatively evaluated, but a set of reference spectra with all the three possible Mn valences needs to be deliberately selected and considered in the fitting. Although the fluorescence signals suffer the self-absorption distortion, the multiplet calculations could consider the distortion effect, which allows a quantitative determination of the overall Ni oxidation state in the bulk. With the aid of multiplet calculations, one could also achieve a quasi-quantitative analysis of the Co redox evolution in LiCoO 2 based on the energy position of the spectroscopic peak. The benefit of multiplet calculations is more important for studying electrode materials with TMs of mixed spin states, as exemplified by the quantitative analysis of the mixed spin Na 2−x Fe 2 (CN) 6 system. At the end, we showcase that such quantitative analysis could provide valuable information for optimizing the electrochemical performance of Na 0.44 MnO 2 electrodes for Na-ion batteries. The methodology summarized in this review could be extended to other energy application systems with TM redox centre for detailed analysis, for example, fuel cell and catalytic materials. (topical review)

Redox Behavior of Fe2+/Fe3+ Redox Couple by Absorption Spectroscopy and Measurement

International Nuclear Information System (INIS)

Oh, J. Y.; Park, S.; Yun, J. I.

2010-01-01

Redox behavior has influences on speciation and other geochemical reactions of radionuclides such as sorption, solubility, and colloid formation, etc. It is one of the factors for evaluation of long-term safety assessment under high-level radioactive waste (HLW) disposal conditions. Accordingly, redox potential (Eh) measurement in aquatic system is important to investigate the redox conditions. Eh is usually measured with redox active electrodes (Pt, Au, glassy carbon, etc.). Nevertheless, Eh measurements by general methods using electrodes provide low accuracy and high uncertainty problem. Therefore, Eh calculated from the concentration of redox active elements with a proper complexing reagent by using UV-Vis absorption spectroscopy is progressed. Iron exists mostly as spent nuclear waste container material and in hydro-geologic minerals. In this system, iron controls the redox condition in near-field area and influences chemical behavior and speciation of radionuclides including redox sensitive actinides such as U, Np, and Pu. In the present work, we present the investigation on redox phenomena of iron in aquatic system by a combination of absorption spectroscopy and redox potential measurements

Review on anionic redox for high-capacity lithium- and sodium-ion batteries

International Nuclear Information System (INIS)

Zhao, Chenglong; Lu, Yaxiang; Hu, Yong-Sheng; Chen, Liquan; Wang, Qidi; Li, Baohua

2017-01-01

Rechargeable batteries, especially lithium-ion batteries, are now widely used as power sources for portable electronics and electric vehicles, but material innovations are still needed to satisfy the increasing demand for larger energy density. Recently, lithium- and sodium-rich electrode materials, including the A 2 MO 3 -family layered compounds (A  =  Li, Na; M  =  Mn 4+ , Ru 4+ , etc), have been extensively studied as potential high-capacity electrode materials for a cumulative cationic and anionic redox activity. Negatively charged oxide ions can potentially donate electrons to compensate for the absence of oxidable transition metals as a redox center to further increase the reversible capacity. Understanding and controlling the state-of-the-art anionic redox processes is pivotal for the design of advanced energy materials, highlighted in rechargeable batteries. Hence, experimental and theoretical approaches have been developed to consecutively study the diverting processes, states, and structures involved. In this review, we attempt to present a literature overview and provide insight into the reaction mechanism with respect to the anionic redox processes, proposing some opinions as target oriented. It is hoped that, through this discussion, the search for anionic redox electrode materials with high-capacity rechargeable batteries can be advanced, and practical applications realized as soon as possible. (topical review)

Electrochemical Characteristics of Layered Transition Metal Oxide Cathode Materials for Lithium Ion Batteries: Surface, Bulk Behavior, and Thermal Properties.

Science.gov (United States)

Tian, Chixia; Lin, Feng; Doeff, Marca M

2018-01-16

Layered lithium transition metal oxides, in particular, NMCs (LiNi x Co y Mn z O 2 ) represent a family of prominent lithium ion battery cathode materials with the potential to increase energy densities and lifetime, reduce costs, and improve safety for electric vehicles and grid storage. Our work has focused on various strategies to improve performance and to understand the limitations to these strategies, which include altering compositions, utilizing cation substitutions, and charging to higher than usual potentials in cells. Understanding the effects of these strategies on surface and bulk behavior and correlating structure-performance relationships advance our understanding of NMC materials. This also provides information relevant to the efficacy of various approaches toward ensuring reliable operation of these materials in batteries intended for demanding traction and grid storage applications. In this Account, we start by comparing NMCs to the isostructural LiCoO 2 cathode, which is widely used in consumer batteries. Effects of changing the metal content (Ni, Mn, Co) upon structure and performance of NMCs are briefly discussed. Our early work on the effects of partial substitution of Al, Fe, and Ti for Co on the electrochemical and bulk structural properties is then covered. The original aim of this work was to reduce the Co content (and thus the raw materials cost) and to determine the effect of the substitutions on the electrochemical and bulk structural properties. More recently, we have turned to the application of synchrotron and advanced microscopy techniques to understand both bulk and surface characteristics of the NMCs. Via nanoscale-to-macroscale spectroscopy and atomically resolved imaging techniques, we were able to determine that the surfaces of NMC undergo heterogeneous reconstruction from a layered structure to rock salt under a variety of conditions. Interestingly, formation of rock salt also occurs under abuse conditions. The surface

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.

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.

Anionic Redox Chemistry in Polysulfide Electrode Materials for Rechargeable Batteries.

Science.gov (United States)

Grayfer, Ekaterina D; Pazhetnov, Egor M; Kozlova, Mariia N; Artemkina, Sofya B; Fedorov, Vladimir E

2017-12-22

Classical Li-ion battery technology is based on the insertion of lithium ions into cathode materials involving metal (cationic) redox reactions. However, this vision is now being reconsidered, as many new-generation electrode materials with enhanced reversible capacities operate through combined cationic and anionic (non-metal) reversible redox processes or even exclusively through anionic redox transformations. Anionic participation in the redox reactions is observed in materials with more pronounced covalency, which is less typical for oxides, but quite common for phosphides or chalcogenides. In this Concept, we would like to draw the reader's attention to this new idea, especially, as it applies to transition-metal polychalcogenides, such as FeS 2 , VS 4 , TiS 3 , NbS 3 , TiS 4 , MoS 3 , etc., in which the key role is played by the (S-S) 2- /2 S 2- redox reaction. The exploration and better understanding of the anion-driven chemistry is important for designing advanced materials for battery and other energy-related applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

New Supercapacitors Based on the Synergetic Redox Effect between Electrode and Electrolyte

Directory of Open Access Journals (Sweden)

You Zhang

2016-08-01

Full Text Available Redox electrolytes can provide significant enhancement of capacitance for supercapacitors. However, more important promotion comes from the synergetic effect and matching between the electrode and electrolyte. Herein, we report a novel electrochemical system consisted of a polyanilline/carbon nanotube composite redox electrode and a hydroquinone (HQ redox electrolyte, which exhibits a specific capacitance of 7926 F/g in a three-electrode system when the concentration of HQ in H2SO4 aqueous electrolyte is 2 mol/L, and the maximum energy density of 114 Wh/kg in two-electrode symmetric configuration. Moreover, the specific capacitance retention of 96% after 1000 galvanostatic charge/discharge cycles proves an excellent cyclic stability. These ultrahigh performances of the supercapacitor are attributed to the synergistic effect both in redox polyanilline-based electrolyte and the redox hydroquinone electrode.

Redox regulation of cell proliferation: Bioinformatics and redox proteomics approaches to identify redox-sensitive cell cycle regulators.

Science.gov (United States)

Foyer, Christine H; Wilson, Michael H; Wright, Megan H

2018-03-29

Plant stem cells are the foundation of plant growth and development. The balance of quiescence and division is highly regulated, while ensuring that proliferating cells are protected from the adverse effects of environment fluctuations that may damage the genome. Redox regulation is important in both the activation of proliferation and arrest of the cell cycle upon perception of environmental stress. Within this context, reactive oxygen species serve as 'pro-life' signals with positive roles in the regulation of the cell cycle and survival. However, very little is known about the metabolic mechanisms and redox-sensitive proteins that influence cell cycle progression. We have identified cysteine residues on known cell cycle regulators in Arabidopsis that are potentially accessible, and could play a role in redox regulation, based on secondary structure and solvent accessibility likelihoods for each protein. We propose that redox regulation may function alongside other known posttranslational modifications to control the functions of core cell cycle regulators such as the retinoblastoma protein. Since our current understanding of how redox regulation is involved in cell cycle control is hindered by a lack of knowledge regarding both which residues are important and how modification of those residues alters protein function, we discuss how critical redox modifications can be mapped at the molecular level. Crown Copyright © 2018. Published by Elsevier Inc. All rights reserved.

Redox sensor proteins for highly sensitive direct imaging of intracellular redox state.

Science.gov (United States)

Sugiura, Kazunori; Nagai, Takeharu; Nakano, Masahiro; Ichinose, Hiroshi; Nakabayashi, Takakazu; Ohta, Nobuhiro; Hisabori, Toru

2015-02-13

Intracellular redox state is a critical factor for fundamental cellular functions, including regulation of the activities of various metabolic enzymes as well as ROS production and elimination. Genetically-encoded fluorescent redox sensors, such as roGFP (Hanson, G. T., et al. (2004)) and Redoxfluor (Yano, T., et al. (2010)), have been developed to investigate the redox state of living cells. However, these sensors are not useful in cells that contain, for example, other colored pigments. We therefore intended to obtain simpler redox sensor proteins, and have developed oxidation-sensitive fluorescent proteins called Oba-Q (oxidation balance sensed quenching) proteins. Our sensor proteins derived from CFP and Sirius can be used to monitor the intracellular redox state as their fluorescence is drastically quenched upon oxidation. These blue-shifted spectra of the Oba-Q proteins enable us to monitor various redox states in conjunction with other sensor proteins. Copyright © 2015 Elsevier Inc. All rights reserved.

Changes in redox properties of humic acids upon sorption to alumina

Science.gov (United States)

Subdiaga, Edisson; Orsetti, Silvia; Jindal, Sharmishta; Haderlein, Stefan B.

2016-04-01

1. Introduction A prominent role of Natural Organic Matter (NOM) in biogeochemical processes is its ability to act as an electron shuttle, accelerating rates between a bulk electron donor and an acceptor. The underlying processes are reversible redox reactions of quinone moieties.1 This shuttling effect has been studied in two major areas: transformation of redox active pollutants and microbial respiration.2-3 Previous studies primarily compared effects in the presence or absence of NOM without addressing the redox properties of NOM nor its speciation. The interaction between humic acids (HA) and minerals might change properties and reactivity of organic matter. Specifically, we investigate whether changes in the redox properties of a HA occur upon sorption to redox inactive minerals. Since fractionation and conformational rearrangements of NOM moieties upon sorption are likely to happen, the redox properties of the NOM fractions upon sorption might differ as well. 2. Materials and methods Elliot Soil Humic Acid (ESHA), Pahokee Peat Humic Acid (PPHA) and Suwannee River Humic Acid (SRHA) were used as received from IHSS. Aluminum oxide (Al2O3) was suspended in 0.1M KCl. Sorption was studied at pH 7.0 in duplicate batch experiments for several HA/Al2O3 ratios. For the suspension (mineral + sorbed HA, plus dissolved HA), the filtrate (0.45μm) and the HA stock solution, the electron donating and accepting capacities (EDC and EAC) were determined following established procedures.4 3. Results All studied HA-Al2O3 systems showed similar behavior with regard to changes in redox properties. There was a significant increase in the EDC of the whole suspension compared to the stock solutions and the non-sorbed HA in the filtrate (up to 300% for PPHA). This effect was more pronounced with increasing amounts of sorbed HA in the suspension. Although ESHA had the highest sorption capacity on Al2O3 (~ 6 times higher than PPHA & SRHA), it showed the smallest changes in redox

Fundamental studies of uranium and neptunium redox flow batteries (II)

International Nuclear Information System (INIS)

Shiokawa, Y.; Yamamura, T.; Watanabe, N.

2002-01-01

The atomic power generation entails production of so-called minor actinides and accumulation of depleted uranium. The theoretical and experimental investigations are underway to transmute minor actinides for minimizing the long-term radiotoxicity and reducing the radioactive waste. The utilization, however, would be alternative means. The actinide redox couples, An(VI)/An(V) and An(IV)/An(III), have excellent properties as battery active materials. Here j the uranium and neptunium redox flow batteries for the electric power storage are discussed from the electrochemical properties of U, Np, Pu and Am [1,2]. One of the required properties for the batteries for electric power storage is high energy efficiency, which is defined by the ratio of the discharge energy to the charge energy. These energies are dependent on the rapidness of kinetics in the electrode reactions, namely the standard rate constants and also the internal resistance of the battery

Redox Regulation of Mitochondrial Function

Science.gov (United States)

Handy, Diane E.

2012-01-01

Abstract Redox-dependent processes influence most cellular functions, such as differentiation, proliferation, and apoptosis. Mitochondria are at the center of these processes, as mitochondria both generate reactive oxygen species (ROS) that drive redox-sensitive events and respond to ROS-mediated changes in the cellular redox state. In this review, we examine the regulation of cellular ROS, their modes of production and removal, and the redox-sensitive targets that are modified by their flux. In particular, we focus on the actions of redox-sensitive targets that alter mitochondrial function and the role of these redox modifications on metabolism, mitochondrial biogenesis, receptor-mediated signaling, and apoptotic pathways. We also consider the role of mitochondria in modulating these pathways, and discuss how redox-dependent events may contribute to pathobiology by altering mitochondrial function. Antioxid. Redox Signal. 16, 1323–1367. PMID:22146081

Photoinduced electron transfer from organic semiconductors onto redox mediators for CO2

International Nuclear Information System (INIS)

Portenkirchner, E.

2014-01-01

In this work the photoinduced electron transfer from organic semiconductors onto redox mediator catalysts for CO 2 reduction has been investigated. In the beginning, the work focuses on the identication, characterization and test of suitable catalyst materials. For this purpose, rhenium compounds with 2,2'-bipyridine bis(arylimino) acenaphthene ligands and pyridinium were tested for molecular homogenous catalysis. Infrared, ultraviolet-visible (UV-Vis) and nuclear magnetic resonance (NMR) spectroscopy were used for initial characterization of the catalyst substances. Since the interpretation of infrared spectra was difficult for large molecules based on measured data only, additionally infrared absorption spectra obtained by quantum mechanical density functional theory(DFT) calculations were successfully used to correlate characteristic features in the measured spectra to their molecular origin. It was found that experimentally observed data and quantum chemical predictions for the infrared spectra of the novel compounds are in good agreement. Additionally, quantum mechanical calculations were carried out for the determination of molecular orbital frontier energy levels and correlated to UV-Vis absorption and cyclic voltammetry measurements. Extensive cyclic voltammetry measurements and bulk controlled-potential electrolysis experiments were performed using a N 2 - and CO 2 -saturated electrolyte solution. Together with a detailed product analysis via infrared spectroscopy, gas and ion chromatography the results allowed electrochemical characterizations of the novel catalysts regarding their suitability for electrochemical CO 2 reduction. Once suitable catalysts were identied, the materials were immobilized on the electrode surface by electro-polymerization of the catalyst (5,5'bisphenylethynyl-2,2'-bipyridyl)Re(CO) 3 Cl itself or by incorporation of (2,2'-bipyridyl)Re(CO) 3 Cl into a polypyrrole matrix, thereby changing from homogeneous to

Effect of organic additives on positive electrolyte for vanadium redox battery

International Nuclear Information System (INIS)

Li Sha; Huang Kelong; Liu Suqin; Fang Dong; Wu Xiongwei; Lu Dan; Wu Tao

2011-01-01

Highlights: → Four organics as electrolyte additives of vanadium redox battery. → Changes are examined in the electrochemical properties of vanadium redox battery. → D-sorbitol is a suitable additive to the electrolyte for the vanadium redox battery. → The mechanism of improvement is discussed in detail. - Abstract: Fructose, mannitol, glucose, D-sorbitol are explored as additives in electrolyte for vanadium redox battery (VRB), respectively. The effects of additives on electrolyte are studied by cyclic voltammetry (CV), charge-discharge technique, electrochemical impedance spectroscopy (EIS) and Raman spectroscopy. The results indicate that the vanadium redox cell using the electrolyte with the additive of D-sorbitol exhibits the best electrochemical performance (the energy efficiency 81.8%). The EIS results indicate that the electrochemical activity of the electrolyte is improved by adding D-sorbitol, which can be interpreted as the increase of available (-OH) groups providing active sites for electron transfer. The Raman spectra show that VO 2+ ions take part in forming a complex with the D-sorbitol, which not only improve solubility of V(V) electrolyte, but also provide more activity sites for the V(IV)/V(V) redox reaction.

Effect of organic additives on positive electrolyte for vanadium redox battery

Energy Technology Data Exchange (ETDEWEB)

Li Sha [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Huang Kelong, E-mail: lisha_csu@163.com [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); Liu Suqin; Fang Dong; Wu Xiongwei; Lu Dan; Wu Tao [Department of Functional Materials and Chemistry, School of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

2011-06-30

Highlights: > Four organics as electrolyte additives of vanadium redox battery. > Changes are examined in the electrochemical properties of vanadium redox battery. > D-sorbitol is a suitable additive to the electrolyte for the vanadium redox battery. > The mechanism of improvement is discussed in detail. - Abstract: Fructose, mannitol, glucose, D-sorbitol are explored as additives in electrolyte for vanadium redox battery (VRB), respectively. The effects of additives on electrolyte are studied by cyclic voltammetry (CV), charge-discharge technique, electrochemical impedance spectroscopy (EIS) and Raman spectroscopy. The results indicate that the vanadium redox cell using the electrolyte with the additive of D-sorbitol exhibits the best electrochemical performance (the energy efficiency 81.8%). The EIS results indicate that the electrochemical activity of the electrolyte is improved by adding D-sorbitol, which can be interpreted as the increase of available (-OH) groups providing active sites for electron transfer. The Raman spectra show that VO{sup 2+} ions take part in forming a complex with the D-sorbitol, which not only improve solubility of V(V) electrolyte, but also provide more activity sites for the V(IV)/V(V) redox reaction.

Geochemistry of Natural Redox Fronts

International Nuclear Information System (INIS)

Hofmann, B.A.

1999-05-01

Redox fronts are important geochemical boundaries which need to be considered in safety assessment of deep repositories for radioactive waste. In most cases, selected host-rock formations will be reducing due to the presence of ferrous minerals, sulphides, etc. During construction and operation of the repository, air will be introduced into the formation. After repository closure, oxidising conditions may persist locally until all oxygen is consumed. In the case of high-level waste, radiolysis of water may provide an additional source of oxidants. Oxidising conditions within a repository are thus possible and potentially have a strong influence on the mobility of many elements. The rate of movement of redox fronts, the boundary between oxidising and reducing environments, and their influence on migrating radionuclides are thus important factors influencing repository performance. The present report is a review of elemental behaviour at natural redox fronts, based on published information and work of the author. Redox fronts are geochemically and geometrically variable manifestations of a global interface between generally oxidising geochemical milieux in contact with the atmosphere and generally reducing milieux in contact with rocks containing ferrous iron, sulphide and/or organic carbon. A classification of redox fronts based on a subdivision into continental near-surface, marine near-surface, and deep environments is proposed. The global redox interface is often located close to the surface of rocks and sediments and, sometimes, within bodies of water. Temperature conditions are close to ambient. A deeper penetration of the global redox front to depths of several kilometres is found in basins containing oxidised sediments (red beds) and in some hydrothermal circulation systems. Temperatures at such deep redox fronts may reach 200 o C. Both near-surface and deep redox fronts are sites of formation of economic deposits of redox-sensitive elements, particularly of

Redox signaling in plants.

Science.gov (United States)

Foyer, Christine H; Noctor, Graham

2013-06-01

Our aim is to deliver an authoritative and challenging perspective of current concepts in plant redox signaling, focusing particularly on the complex interface between the redox and hormone-signaling pathways that allow precise control of plant growth and defense in response to metabolic triggers and environmental constraints and cues. Plants produce significant amounts of singlet oxygen and other reactive oxygen species (ROS) as a result of photosynthetic electron transport and metabolism. Such pathways contribute to the compartment-specific redox-regulated signaling systems in plant cells that convey information to the nucleus to regulate gene expression. Like the chloroplasts and mitochondria, the apoplast-cell wall compartment makes a significant contribution to the redox signaling network, but unlike these organelles, the apoplast has a low antioxidant-buffering capacity. The respective roles of ROS, low-molecular antioxidants, redox-active proteins, and antioxidant enzymes are considered in relation to the functions of plant hormones such as salicylic acid, jasmonic acid, and auxin, in the composite control of plant growth and defense. Regulation of redox gradients between key compartments in plant cells such as those across the plasma membrane facilitates flexible and multiple faceted opportunities for redox signaling that spans the intracellular and extracellular environments. In conclusion, plants are recognized as masters of the art of redox regulation that use oxidants and antioxidants as flexible integrators of signals from metabolism and the environment.

Electron Transfer in Flavodoxin-based Redox Maquettes

NARCIS (Netherlands)

Alagaratnam, S.

2005-01-01

Small redox proteins play the role of electron taxis in the cell, picking electrons up at one location and delivering them at another. While it is known that these reactions are the basis for the processes of energy generation by respiration and photosynthesis, the means by which these 'taxis'

Design of solar drying-plant for bulk material drying

Directory of Open Access Journals (Sweden)

Peter Horbaj

2008-11-01

Full Text Available A generally well-known high energy requirement for technological processes of drying and the fact that the world’s supplyof the conventional energy sources has considerably decreased are the decisive factors forcing us to look for some new, if possible,renewable energy sources for this process by emphasising their environmental reliability. One of the possibilities how to replace, atleast partly, the conventional energy sources – heat in a drying process is solar energy.Air-drying of bulk materials usually has a series of disadvantages such as time expenditure, drying defects in the bulk materialand inadequate final moisture content. A method that obviates or reduces the disadvantages of air-drying and, at the same time, reducesthe costs of kiln drying, is drying with solar heat. Solar energy can replace a large part of this depletable energy since solar energy cansupply heat at the temperatures most often used to dry bulk material. Solar drying-plant offer an attractive solution.

Intermittent fasting results in tissue-specific changes in bioenergetics and redox state.

Science.gov (United States)

Chausse, Bruno; Vieira-Lara, Marcel A; Sanchez, Angélica B; Medeiros, Marisa H G; Kowaltowski, Alicia J

2015-01-01

Intermittent fasting (IF) is a dietary intervention often used as an alternative to caloric restriction (CR) and characterized by 24 hour cycles alternating ad libitum feeding and fasting. Although the consequences of CR are well studied, the effects of IF on redox status are not. Here, we address the effects of IF on redox state markers in different tissues in order to uncover how changes in feeding frequency alter redox balance in rats. IF rats displayed lower body mass due to decreased energy conversion efficiency. Livers in IF rats presented increased mitochondrial respiratory capacity and enhanced levels of protein carbonyls. Surprisingly, IF animals also presented an increase in oxidative damage in the brain that was not related to changes in mitochondrial bioenergetics. Conversely, IF promoted a substantial protection against oxidative damage in the heart. No difference in mitochondrial bioenergetics or redox homeostasis was observed in skeletal muscles of IF animals. Overall, IF affects redox balance in a tissue-specific manner, leading to redox imbalance in the liver and brain and protection against oxidative damage in the heart.

Intermittent fasting results in tissue-specific changes in bioenergetics and redox state.

Directory of Open Access Journals (Sweden)

Bruno Chausse

Full Text Available Intermittent fasting (IF is a dietary intervention often used as an alternative to caloric restriction (CR and characterized by 24 hour cycles alternating ad libitum feeding and fasting. Although the consequences of CR are well studied, the effects of IF on redox status are not. Here, we address the effects of IF on redox state markers in different tissues in order to uncover how changes in feeding frequency alter redox balance in rats. IF rats displayed lower body mass due to decreased energy conversion efficiency. Livers in IF rats presented increased mitochondrial respiratory capacity and enhanced levels of protein carbonyls. Surprisingly, IF animals also presented an increase in oxidative damage in the brain that was not related to changes in mitochondrial bioenergetics. Conversely, IF promoted a substantial protection against oxidative damage in the heart. No difference in mitochondrial bioenergetics or redox homeostasis was observed in skeletal muscles of IF animals. Overall, IF affects redox balance in a tissue-specific manner, leading to redox imbalance in the liver and brain and protection against oxidative damage in the heart.

Electrochemical redox processes involving soluble cerium species

International Nuclear Information System (INIS)

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

2016-01-01

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

A solar rechargeable flow battery based on photoregeneration of two soluble redox couples.

Science.gov (United States)

Liu, Ping; Cao, Yu-liang; Li, Guo-Ran; Gao, Xue-Ping; Ai, Xin-Ping; Yang, Han-Xi

2013-05-01

Storable sunshine, reusable rays: A solar rechargeable redox flow battery is proposed based on the photoregeneration of I(3)(-)/I(-) and [Fe(C(10)H(15))(2)](+)/Fe(C(10)H(15))(2) soluble redox couples, which can be regenerated by flowing from a discharged redox flow battery (RFB) into a dye-sensitized solar cell (DSSC) and then stored in tanks for subsequent RFB applications This technology enables effective solar-to-chemical energy conversion. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-01-01

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, nonaqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of nonaqueous electrolytes. However, significant technical hurdles exist currently limiting nonaqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we report a nonaqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox materials exhibits an ambipolar electrochemical property with two reversible redox pairs that are moderately separated by a voltage gap of ~1.7 V. Therefore, PTIO can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry, which affords the advantages such as high effective redox concentrations and low irreversible redox material crossover. The PTIO flow battery shows decent electrochemical cyclability under cyclic voltammetry and flow cell conditions; an improved redox concentration of 0.5 M PTIO and operational current density of 20 mA cm-2 were achieved in flow cell tests. Moreover, we show that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC) as cross-validated by electron spin resonance measurements. This study suggests FTIR can be used as a reliable online SOC sensor to monitor flow battery status and ensure battery operations stringently in a safe SOC range.

Measurement of the Structure and Molecular Dynamics of Ionic Solutions for Redox Flow Battery

Science.gov (United States)

Li, Zhixia; Robertson, Lily; Moore, Jeffery; Zhang, Yang

Redox flow battery (RFB) is a promising electrical energy storage technology with great potential to finally realize alternative energy sources for the next-generation vehicles and at grid scales. The design of RFB is unique as the power scales separately from the energy capacity. The latter depends on the size of storage tanks and the concentration of the active materials. Redox-active organic molecules are excellent candidates with high synthetic tunability for both redox properties as well as, importantly, solubility. However, upon increasing concentrations, the flow cell has less cycling stability and more capacity fade. Further, after charging the battery, the viscosity increases while the ionic conductivity decreases, and thus the cell becomes overall ineffective. To understand the mechanism of the increased viscosity, we performed differential scanning calorimetry, wide and small angle X-rays scattering, and quasi-elastic neutron scattering measurements. Herein, we will present the measurement results and relative analysis.

Redox Kinetics and Nonstoichiometry of Ce0.5Zr0.5O2−δ for Water Splitting and Hydrogen Production

KAUST Repository

Zhao, Zhenlong

2017-04-25

Water splitting and chemical fuel production as a promising carbon-neutral energy solution relies critically on an efficient electrochemical process over catalyst surfaces. The fundamentals within the surface redox pathways, including the complex interactions of mobile ions and electrons between the bulk and the surface, along with the role of adsorbates and electrostatic fields remain yet to be understood quantitatively. This work presents a detailed kinetics study and nonstoichiometry characterization of Ce0.5Zr0.5O2−δ (CZO), one of the most recognized catalysts for water splitting. The use of CZO leads to >60% improvement in the kinetic rates as compared with undoped ceria with twice the total yield at 700 °C, resulting from the improved reducibility. The peak H2 production rate is 95 μmol g–1 s–1 at 700 °C, and the total production is 750 μmol g–1. A threshold temperature of 650 °C is required to achieve significant H2 production at fast rates. The redox kinetics is modeled using two-step surface chemistry with bulk-to-surface transport equilibrium. Kinetics and equilibrium parameters are extracted, and the model predictions show good agreement with the measurements. The enthalpy of bulk defect formation for CZO is found to be 262 kJ/mol, >40% lower than that of undoped ceria. As oxygen vacancy is gradually filled up, the surface H2O splitting chemistry undergoes a transition from exothermic to endothermic, with the crossover around δ = 0.04 to 0.05, which constrains the further ion incorporation process. Our kinetics study reveals that the H2O splitting process with CZO is kinetics limited at low temperature and transitions to partial-equilibrium with significantly enhanced backward reaction at high temperature. The charge-transfer step is found to be the rate-limiting step for H2O splitting. The detailed kinetics and nonstoichiometric equilibria should be helpful in guiding the design and optimization of CZO as a catalyst, oxygen storage

Effect of the Linker in Terephthalate-Functionalized Conducting Redox Polymers

International Nuclear Information System (INIS)

Yang, Li; Huang, Xiao; Gogoll, Adolf; Strømme, Maria; Sjödin, Martin

2016-01-01

The combination of high capacity redox active pendent groups and conducting polymers, realized in conducting redox polymers (CRPs), provides materials with high charge storage capacity that are electronically conducting which makes CRPs attractive for electrical energy storage applications. In this report, six polythiophene and poly(3,4-ethylenedioxythiophene)(PEDOT)-based CRPs with a diethyl terephthalate unit covalently bound to the polymer chain by various linkers have been synthesized and characterized electrochemically. The effects of the choice of polymer backbone and of the nature of the link on the electrochemistry, and in particular the cycling stability of these polymers, are discussed. All CRPs show both the doping of the polymer backbone as well as the redox behavior of the pendent groups and the redox potential of the pendent groups in the CRPs is close to that of corresponding monomer, indicating insignificant interaction between the pendant and the polymer backbone. While all CRPs show various degrees of charge decay upon electrochemical redox conversion, the PEDOT-based CRPs show significantly improved stability compared to the polythiophene counterparts. Moreover, we show that by the right choice of link the cycling stability of diethyl terephthalate substituted PEDOT-based CRPs can be significantly improved.

High energy photoelectron spectroscopy in basic and applied science: Bulk and interface electronic structure

Energy Technology Data Exchange (ETDEWEB)

Knut, Ronny; Lindblad, Rebecka [Department of Physics and Astronomy, Uppsala University, SE-751 21 Uppsala (Sweden); Gorgoi, Mihaela [Helmholtz Zentrum Berlin für Materialien und Energie GmbH, Albert-Einstein-Str. 15, 12489 Berlin (Germany); Rensmo, Håkan [Department of Physics and Astronomy, Uppsala University, SE-751 21 Uppsala (Sweden); Karis, Olof, E-mail: olof.karis@physics.uu.se [Department of Physics and Astronomy, Uppsala University, SE-751 21 Uppsala (Sweden)

2013-10-15

Highlights: •We demonstrate how hard X-ray photoelectron spectroscopy can be used to investigate interface properties of multilayers. •By combining HAXPES and statistical methods we are able to provide quantitative analysis of the interface diffusion process. •We show how photoionization cross sections can be used to map partial density of states contributions to valence states. •We use HAXPES to provide insight into the valence electronic structure of e.g. multiferroics and dye-sensitized solar cells. -- Abstract: With the access of new high-performance electron spectrometers capable of analyzing electron energies up to the order of 10 keV, the interest for photoelectron spectroscopy has grown and many new applications of the technique in areas where electron spectroscopies were considered to have limited use have been demonstrated over the last few decades. The technique, often denoted hard X-ray photoelectron spectroscopy (HX-PES or HAXPES), to distinguish the experiment from X-ray photoelectron spectroscopy performed at lower energies, has resulted in an increasing interest in photoelectron spectroscopy in many areas. The much increased mean free path at higher kinetic energies, in combination with the elemental selectivity of the core level spectroscopies in general has led to this fact. It is thus now possible to investigate the electronic structure of materials with a substantially enhanced bulk sensitivity. In this review we provide examples from our own research using HAXPES which to date has been performed mainly at the HIKE facility at the KMC-1 beamline at HZB, Berlin. The review exemplifies the new opportunities using HAXPES to address both bulk and interface electronic properties in systems relevant for applications in magnetic storage, energy related research, but also in purely curiosity driven problems.

High energy photoelectron spectroscopy in basic and applied science: Bulk and interface electronic structure

International Nuclear Information System (INIS)

Knut, Ronny; Lindblad, Rebecka; Gorgoi, Mihaela; Rensmo, Håkan; Karis, Olof

2013-01-01

Highlights: •We demonstrate how hard X-ray photoelectron spectroscopy can be used to investigate interface properties of multilayers. •By combining HAXPES and statistical methods we are able to provide quantitative analysis of the interface diffusion process. •We show how photoionization cross sections can be used to map partial density of states contributions to valence states. •We use HAXPES to provide insight into the valence electronic structure of e.g. multiferroics and dye-sensitized solar cells. -- Abstract: With the access of new high-performance electron spectrometers capable of analyzing electron energies up to the order of 10 keV, the interest for photoelectron spectroscopy has grown and many new applications of the technique in areas where electron spectroscopies were considered to have limited use have been demonstrated over the last few decades. The technique, often denoted hard X-ray photoelectron spectroscopy (HX-PES or HAXPES), to distinguish the experiment from X-ray photoelectron spectroscopy performed at lower energies, has resulted in an increasing interest in photoelectron spectroscopy in many areas. The much increased mean free path at higher kinetic energies, in combination with the elemental selectivity of the core level spectroscopies in general has led to this fact. It is thus now possible to investigate the electronic structure of materials with a substantially enhanced bulk sensitivity. In this review we provide examples from our own research using HAXPES which to date has been performed mainly at the HIKE facility at the KMC-1 beamline at HZB, Berlin. The review exemplifies the new opportunities using HAXPES to address both bulk and interface electronic properties in systems relevant for applications in magnetic storage, energy related research, but also in purely curiosity driven problems

A general approach toward enhancement of pseudocapacitive performance of conducting polymers by redox-active electrolytes

KAUST Repository

Chen, Wei

2014-12-01

A general approach is demonstrated where the pseudocapacitive performance of different conducting polymers is enhanced in redox-active electrolytes. The concept is demonstrated using several electroactive conducting polymers, including polyaniline, polypyrrole, and poly(3,4-ethylenedioxythiophene). As compared to conventional electrolytes, the redox-active electrolytes, prepared by simply adding a redox mediator to the conventional electrolyte, can significantly improve the energy storage capacity of pseudocapacitors with different conducting polymers. The results show that the specific capacitance of conducting polymer based pseudocapacitors can be increased by a factor of two by utilization of the redox-active electrolytes. In fact, this approach gives some of the highest reported specific capacitance values for electroactive conducting polymers. Moreover, our findings present a general and effective approach for the enhancement of energy storage performance of pseudocapacitors using a variety of polymeric electrode materials. © 2014 Elsevier B.V. All rights reserved.

In situ scanning tunnelling microscopy of redox molecules. Coherent electron transfer at large bias voltages

DEFF Research Database (Denmark)

Zhang, Jingdong; Kuznetsov, A.M.; Ulstrup, Jens

2003-01-01

Theories of in situ scanning tunnelling microscopy (STM) of molecules with redox levels near the substrate and tip Fermi levels point to 'spectroscopic' current-overpotential features. Prominent features require a narrow 'probing tip', i.e. a small bias voltage, eV(bias), compared...... a broad tunnelling current-overpotential range at a constant (large) bias voltage of +0.2 V. The current is found to be constant over a 0.25 V overpotential range, which covers roughly the range where the oxidised and reduced redox levels are located within the energy tip. STM contrast and apparent...... of previous theoretical work on in situ STM of redox molecules, to large bias voltages, \\eV(bias)\\ > E-r. Large bias voltages give tunnelling contrasts independent of the overpotential over a broad range, as both the oxidised and reduced redox levels are located within the 'energy tip' between the substrate...

Sediment phosphorus speciation and mobility under dynamic redox conditions

Science.gov (United States)

Parsons, Chris T.; Rezanezhad, Fereidoun; O'Connell, David W.; Van Cappellen, Philippe

2017-07-01

Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O2) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N2), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous- and solid-phase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low ( ˜ 2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl2 and NaHCO3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h-1 kg-1 indicated the potential for rapid mineralization of organic P (Po), in particular during periods of aeration when the

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

Science.gov (United States)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-12-23

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

Science.gov (United States)

Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

2016-01-01

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering

Science.gov (United States)

Yang, Wanli; Devereaux, Thomas P.

2018-06-01

Recent advances in battery science and technology have triggered both the challenges and opportunities on studying the materials and interfaces in batteries. Here, we review the recent demonstrations of soft X-ray spectroscopy for studying the interfaces and electrode materials. The focus of this review is on the recently developed mapping of resonant inelastic X-ray scattering (mRIXS) as a powerful probe of battery chemistry with superior sensitivity. Six different channels of soft X-ray absorption spectroscopy (sXAS) are introduced for different experimental purposes. Although conventional sXAS channels remain effective tools for quantitative analysis of the transition-metal states and surface chemistry, we elaborate the limitations of sXAS in both cationic and anionic redox studies. Particularly, based on experimental findings in various electrodes, we show that sXAS is unreliable for studying oxygen redox. We then demonstrate the mRIXS as a reliable technique for fingerprinting oxygen redox and summarize several crucial observations. We conclude that mRIXS is the tool-of-choice to study both the practical issue on reversibility of oxygen redox and the fundamental nature of bulk oxygen states. We hope this review clarifies the popular misunderstanding on oxygen sXAS results of oxide electrodes, and establishes a reliable technique for detecting oxygen redox through mRIXS.

Bulk viscosity, interaction and the viability of phantom solutions

Energy Technology Data Exchange (ETDEWEB)

Leyva, Yoelsy; Sepulveda, Mirko [Universidad de Tarapaca, Departamento de Fisica, Facultad de Ciencias, Arica (Chile)

2017-06-15

We study the dynamics of a bulk viscosity model in the Eckart approach for a spatially flat Friedmann-Robertson-Walker (FRW) Universe. We have included radiation and dark energy, assumed as perfect fluids, and dark matter treated as an imperfect fluid having bulk viscosity. We also introduce an interaction term between the dark matter and dark energy components. Considering that the bulk viscosity is proportional to the dark matter energy density and imposing a complete cosmological dynamics, we find bounds on the bulk viscosity in order to reproduce a matter-dominated era (MDE). This constraint is independent of the interaction term. Some late time phantom solutions are mathematically possible. However, the constraint imposed by a MDE restricts the interaction parameter, in the phantom solutions, to a region consistent with a null value, eliminating the possibility of late time stable solutions with w < -1. From the different cases that we study, the only possible scenario, with bulk viscosity and interaction term, belongs to the quintessence region. In the latter case, we find bounds on the interaction parameter compatible with latest observational data. (orig.)

Observation of core-level binding energy shifts between (100) surface and bulk atoms of epitaxial CuInSe2

International Nuclear Information System (INIS)

Nelson, A.J.; Berry, G.; Rockett, A.

1997-01-01

Core-level and valence band photoemission from semiconductors has been shown to exhibit binding energy differences between surface atoms and bulk atoms, thus allowing one to unambiguously distinguish between the two atomic positions. Quite clearly, surface atoms experience a potential different from the bulk due to the lower coordination number - a characteristic feature of any surface is the incomplete atomic coordination. Theoretical accounts of this phenomena are well documented in the literature for III-V and II-VI semiconductors. However, surface state energies corresponding to the equilibrium geometry of (100) and (111) surfaces of Cu-based ternary chalcopyrite semiconductors have not been calculated or experimental determined. These compounds are generating great interest for optoelectronic and photovoltaic applications, and are an isoelectronic analog of the II-VI binary compound semiconductors. Surface core-level binding energy shifts depend on the surface cohesive energies, and surface cohesive energies are related to surface structure. For ternary compound semiconductor surfaces, such as CuInSe 2 , one has the possibility of variations in surface stoichiometry. Applying standard thermodynamical calculations which consider the number of individual surface atoms and their respective chemical potentials should allow one to qualitatively determine the magnitude of surface core-level shifts and, consequently, surface state energies

Neuronal redox imbalance results in altered energy homeostasis and early postnatal lethality.

Science.gov (United States)

Maity-Kumar, Gandhari; Thal, Dietmar R; Baumann, Bernd; Scharffetter-Kochanek, Karin; Wirth, Thomas

2015-07-01

Redox imbalance is believed to contribute to the development and progression of several neurodegenerative disorders. Our aim was to develop an animal model that exhibits neuron-specific oxidative stress in the CNS to study the consequences and eventually find clues regarding the pathomechanisms of oxidative insults in neuronal homeostasis. We therefore generated a novel neuron-specific superoxide dismutase 2 (SOD2)-deficient mouse by deleting exon 3 of the SOD2 gene using CamKIIα promoter-driven Cre expression. These neuron-specific SOD2 knockout (SOD2(nko)) mice, although born at normal frequencies, died at the age of 4 weeks with critical growth retardation, severe energy failure, and several neurologic phenotypes. In addition, SOD2(nko) mice exhibited severe neuronal alterations such as reactive astrogliosis, neuronal cell cycle inhibition, and induction of apoptosis. JNK activation and stabilization of p53, as a result of reactive oxygen species accumulation, are most likely the inducers of neuronal apoptosis in SOD2(nko) mice. It is remarkable that hypothalamic regulation of glucose metabolism was affected, which in turn induced necrotic brain lesions in SOD2(nko) mice. Taken together, our findings suggest that exclusive deficiency of SOD2 in neurons results in an impaired central regulation of energy homeostasis that leads to persistent hypoglycemia, hypoglycemia-related neuropathology, and an early lethality of the mutant mice. © FASEB.

Economic analysis of a new class of vanadium redox-flow battery for medium- and large-scale energy storage in commercial applications with renewable energy

International Nuclear Information System (INIS)

Li, Ming-Jia; Zhao, Wei; Chen, Xi; Tao, Wen-Quan

2017-01-01

Highlights: • A new class of the vanadium redox-flow battery (VRB) is developed. • The new class of VRB is more economic. It is simple process and easy to scale-up. • There are three levels of cell stacks and electrolytes with different qualities. • The economic analysis of the VRB system for renewable energy bases is carried out. • Related polices and suggestions based on the result are provided. - Abstract: Interest in the implement of vanadium redox-flow battery (VRB) for energy storage is growing, which is widely applicable to large-scale renewable energy (e.g. wind energy and solar photo-voltaic), developing distributed generation, lowering the imbalance and increasing the usage of electricity. However, a comprehensive economic analysis of the VRB for energy storage is obscured for various commercial applications, yet it is fundamental for implementation of the VRB in commercial electricity markets. In this study, based on a new class of the VRB that was developed by our team, a comprehensive economic analysis of the VRB for large-scale energy storage is carried out. The results illustrate the economy of the VRB applications for three typical energy systems: (1) The VRB storage system instead of the normal lead-acid battery to be the uninterrupted power supply (UPS) battery for office buildings and hospitals; (2) Application of vanadium battery in household distributed photo-voltaic power generation systems; (3) The wind power and solar power stations equipped with the VRB storage systems. The economic perspectives and cost-benefit analysis of the VRB storage systems may underpin optimisation for maximum profitability. In this case, two findings are concluded. First, with the fixed capacity power or fixed discharging time, the greater profit ratio will be generated from the longer time or the larger capacity power. Second, when the profit ratio, discharging time and capacity power are all variables, it is necessary to find out the best optimisation

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.

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.

Investigation of the Redox Chemistry of Anthraquinone Derivatives Using Density Functional Theory

Energy Technology Data Exchange (ETDEWEB)

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 are 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 non-aqueous solvent and improve its solubility. Thermochemical calculations for likely bond breaking decomposition reactions of un-substituted AQ anions suggest that the dianions are relatively stable in the solution. These studies provide 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.

Bulk electronic structures of n-type superconductor Nd1.85Ce0.15CuO4 probed by high energy angle-resolved photoemission spectroscopy

International Nuclear Information System (INIS)

Tsunekawa, M.; Sekiyama, A.; Kasai, S.; Yamasaki, A.; Fujiwara, H.; Sing, M.; Shigemoto, A.; Imada, S.; Onose, Y.; Tokura, Y.; Muro, T.; Suga, S.

2005-01-01

We report on a high-energy angle-resolved photoemission (ARPES) study of the n-type high-T C cuprate, Nd 1.85 Ce 0.15 CuO 4 (NCCO). Our bulk sensitive results suggest a hole-like Fermi surface as seen by the so far reported low-energy ARPES studies. The soft X-ray Cu 2p core-level photoemission spectra show clear polar-angle dependence, suggesting the difference in electron states between the bulk and surface

Structural determinants in the bulk heterojunction.

Science.gov (United States)

Acocella, Angela; Höfinger, Siegfried; Haunschmid, Ernst; Pop, Sergiu C; Narumi, Tetsu; Yasuoka, Kenji; Yasui, Masato; Zerbetto, Francesco

2018-02-21

Photovoltaics is one of the key areas in renewable energy research with remarkable progress made every year. Here we consider the case of a photoactive material and study its structural composition and the resulting consequences for the fundamental processes driving solar energy conversion. A multiscale approach is used to characterize essential molecular properties of the light-absorbing layer. A selection of bulk-representative pairs of donor/acceptor molecules is extracted from the molecular dynamics simulation of the bulk heterojunction and analyzed at increasing levels of detail. Significantly increased ground state energies together with an array of additional structural characteristics are identified that all point towards an auxiliary role of the material's structural organization in mediating charge-transfer and -separation. Mechanistic studies of the type presented here can provide important insights into fundamental principles governing solar energy conversion in next-generation photovoltaic devices.

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.

Occurrence and fate of bulk organic matter and pharmaceutically active compounds in managed aquifer recharge: A review

KAUST Repository

Maeng, Sungkyu

2011-05-01

Managed aquifer recharge (MAR) is a natural water treatment process that induces surface water to flow in response to a hydraulic gradient through soil/sediment and into a vertical or horizontal well. It is a relatively cost-effective, robust and sustainable technology. Detailed characteristics of bulk organic matter and the occurrence and fate of pharmaceutically active compounds (PhACs) during MAR processes such as bank filtration (BF) and artificial recharge (AR) were reviewed. Understanding the fate of bulk organic matter during BF and AR is an essential step in determining pre- and/or post-treatment requirements. Analysis of organic matter characteristics using a suite of analytical tools suggests that there is a preferential removal of non-humic substances during MAR. Different classes of PhACs were found to behave differently during BF and AR. Antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), beta blockers, and steroid hormones generally exhibited good removal efficiencies, especially for compounds having hydrophobic-neutral characteristics. However, anticonvulsants showed a persistent behavior during soil passage. There were also some redox-dependent PhACs. For example, X-ray contrast agents measured, as adsorbable organic iodine (AOI), and sulfamethoxazole (an antibiotic) degraded more favorably under anoxic conditions compared to oxic conditions. Phenazone-type pharmaceuticals (NSAIDs) exhibited better removal under oxic conditions. The redox transition from oxic to anoxic conditions during soil passage can enhance the removal of PhACs that are sensitive to redox conditions. In general, BF and AR can be included in a multi-barrier treatment system for the removal of PhACs. © 2011.

Occurrence and fate of bulk organic matter and pharmaceutically active compounds in managed aquifer recharge: a review.

Science.gov (United States)

Maeng, Sung Kyu; Sharma, Saroj K; Lekkerkerker-Teunissen, Karin; Amy, Gary L

2011-05-01

Managed aquifer recharge (MAR) is a natural water treatment process that induces surface water to flow in response to a hydraulic gradient through soil/sediment and into a vertical or horizontal well. It is a relatively cost-effective, robust and sustainable technology. Detailed characteristics of bulk organic matter and the occurrence and fate of pharmaceutically active compounds (PhACs) during MAR processes such as bank filtration (BF) and artificial recharge (AR) were reviewed. Understanding the fate of bulk organic matter during BF and AR is an essential step in determining pre- and/or post-treatment requirements. Analysis of organic matter characteristics using a suite of analytical tools suggests that there is a preferential removal of non-humic substances during MAR. Different classes of PhACs were found to behave differently during BF and AR. Antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), beta blockers, and steroid hormones generally exhibited good removal efficiencies, especially for compounds having hydrophobic-neutral characteristics. However, anticonvulsants showed a persistent behavior during soil passage. There were also some redox-dependent PhACs. For example, X-ray contrast agents measured, as adsorbable organic iodine (AOI), and sulfamethoxazole (an antibiotic) degraded more favorably under anoxic conditions compared to oxic conditions. Phenazone-type pharmaceuticals (NSAIDs) exhibited better removal under oxic conditions. The redox transition from oxic to anoxic conditions during soil passage can enhance the removal of PhACs that are sensitive to redox conditions. In general, BF and AR can be included in a multi-barrier treatment system for the removal of PhACs. Copyright © 2011. Published by Elsevier Ltd.

Bulk substrate porosity verification by applying Monte Carlo modeling and Castaing's formula using energy-dispersive x-rays

Science.gov (United States)

Yung, Lai Chin; Fei, Cheong Choke; Mandeep, Jit Singh; Amin, Nowshad; Lai, Khin Wee

2015-11-01

The leadframe fabrication process normally involves additional thin-metal layer plating on the bulk copper substrate surface for wire bonding purposes. Silver, tin, and copper flakes are commonly adopted as plating materials. It is critical to assess the density of the plated metal layer, and in particular to look for porosity or voids underneath the layer, which may reduce the reliability during high-temperature stress. A fast, reliable inspection technique is needed to assess the porosity or void weakness. To this end, the characteristics of x-rays generated from bulk samples were examined using an energy-dispersive x-ray (EDX) detector to examine the porosity percentage. Monte Carlo modeling was integrated with Castaing's formula to verify the integrity of the experimental data. Samples with different porosity percentages were considered to test the correlation between the intensity of the collected x-ray signal and the material density. To further verify the integrity of the model, conventional cross-sectional samples were also taken to observe the porosity percentage using Image J software measurement. A breakthrough in bulk substrate assessment was achieved by applying EDX for the first time to nonelemental analysis. The experimental data showed that the EDX features were not only useful for elemental analysis, but also applicable to thin-film metal layer thickness measurement and bulk material density determination. A detailed experiment was conducted using EDX to assess the plating metal layer and bulk material porosity.

Redox Mediators for Li-O2 Batteries: Status and Perspectives.

Science.gov (United States)

Park, Jin-Bum; Lee, Seon Hwa; Jung, Hun-Gi; Aurbach, Doron; Sun, Yang-Kook

2018-01-01

Li-O 2 batteries have received much attention due to their extremely large theoretical energy density. However, the high overpotentials required for charging Li-O 2 batteries lower their energy efficiency and degrade the electrolytes and carbon electrodes. This problem is one of the main obstacles in developing practical Li-O 2 batteries. To solve this problem, it is important to facilitate the oxidation of Li 2 O 2 upon charging by using effective electrocatalysis. Using solid catalysts is not too effective for oxidizing the electronically isolating Li-peroxide layers. In turn, for soluble catalysts, red-ox mediators (RMs) are homogeneously dissolved in the electrolyte solutions and can effectively oxidize all of the Li 2 O 2 precipitated during discharge. RMs can decompose solid Li 2 O 2 species no matter their size, morphology, or thickness and thus dramatically increase energy efficiency. However, some negative side effects, such as the shuttle reactions of RMs and deterioration of the Li-metal occur. Therefore, it is necessary to study the activity and stability of RMs in Li-O 2 batteries in detail. Herein, recent studies related to redox mediators are reviewed and the mechanisms of redox reactions are illustrated. The development opportunities of RMs for this important battery technology are discussed and future directions are suggested. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of long-term fertilization on humic redox mediators in multiple microbial redox reactions.

Science.gov (United States)

Guo, Peng; Zhang, Chunfang; Wang, Yi; Yu, Xinwei; Zhang, Zhichao; Zhang, Dongdong

2018-03-01

This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2',4,4',5,5'- hexachlorobiphenyl (PCB 153 ) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB 153 dechlorination activity (1.03 μM PCB 153 removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms' metabolisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Computational assignment of redox states to Coulomb blockade diamonds.

Science.gov (United States)

Olsen, Stine T; Arcisauskaite, Vaida; Hansen, Thorsten; Kongsted, Jacob; Mikkelsen, Kurt V

2014-09-07

With the advent of molecular transistors, electrochemistry can now be studied at the single-molecule level. Experimentally, the redox chemistry of the molecule manifests itself as features in the observed Coulomb blockade diamonds. We present a simple theoretical method for explicit construction of the Coulomb blockade diamonds of a molecule. A combined quantum mechanical/molecular mechanical method is invoked to calculate redox energies and polarizabilities of the molecules, including the screening effect of the metal leads. This direct approach circumvents the need for explicit modelling of the gate electrode. From the calculated parameters the Coulomb blockade diamonds are constructed using simple theory. We offer a theoretical tool for assignment of Coulomb blockade diamonds to specific redox states in particular, and a study of chemical details in the diamonds in general. With the ongoing experimental developments in molecular transistor experiments, our tool could find use in molecular electronics, electrochemistry, and electrocatalysis.

A biomimetic redox flow battery based on flavin mononucleotide.

Science.gov (United States)

Orita, Akihiro; Verde, Michael G; Sakai, Masanori; Meng, Ying Shirley

2016-10-21

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures.

A biomimetic redox flow battery based on flavin mononucleotide

Science.gov (United States)

Orita, Akihiro; Verde, Michael G.; Sakai, Masanori; Meng, Ying Shirley

2016-10-01

The versatility in design of redox flow batteries makes them apt to efficiently store energy in large-scale applications at low cost. The discovery of inexpensive organic electroactive materials for use in aqueous flow battery electrolytes is highly attractive, but is thus far limited. Here we report on a flow battery using an aqueous electrolyte based on the sodium salt of flavin mononucleotide. Flavins are highly versatile electroactive molecules, which catalyse a multitude of redox reactions in biological systems. We use nicotinamide (vitamin B3) as a hydrotropic agent to enhance the water solubility of flavin mononucleotide. A redox flow battery using flavin mononucleotide negative and ferrocyanide positive electrolytes in strong base shows stable cycling performance, with over 99% capacity retention over the course of 100 cycles. We hypothesize that this is enabled due to the oxidized and reduced forms of FMN-Na being stabilized by resonance structures.

Redox and the circadian clock in plant immunity: A balancing act.

Science.gov (United States)

Karapetyan, Sargis; Dong, Xinnian

2018-05-01

Plants' reliance on sunlight for energy makes their light-driven circadian clock a critical regulator in balancing the energy needs for vital activities such as growth and defense. Recent studies show that the circadian clock acts as a strategic planner to prime active defense responses towards the morning or daytime when conditions, such as the opening of stomata required for photosynthesis, are favorable for attackers. Execution of the defense response, on the other hand, is determined according to the cellular redox state and is regulated in part by the production of reactive oxygen and nitrogen species upon pathogen challenge. The interplay between redox and the circadian clock further gates the onset of defense response to a specific time of the day to avoid conflict with growth-related activities. In this review, we focus on discussing the roles of the circadian clock as a robust overseer and the cellular redox as a dynamic executor of plant defense. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

The effects of heating temperatures and time on deformation energy and oil yield of sunflower bulk seeds in compression loading

Science.gov (United States)

Kabutey, A.; Herak, D.; Sigalingging, R.; Demirel, C.

2018-02-01

The deformation energy (J) and percentage oil yield (%) of sunflower bulk seeds under the influence of heat treatment temperatures and heating time were examined in compression test using the universal compression testing machine and vessel diameter of 60 mm with a plunger. The heat treatment temperatures were between 40 and 100 °C and the heating time at specific temperatures of 40 and 100 °C ranged from 15 to 75 minutes. The bulk sunflower seeds were measured at a pressing height of 60 mm and pressed at a maximum force of 100 kN and speed of 5 mm/min. Based on the compression results, the deformation energy and oil yield increased along with increasing heat treatment temperatures. The results were statistically significant (p 0.05).

REDOX IMAGING OF THE p53-DEPENDENT MITOCHONDRIAL REDOX STATE IN COLON CANCER EX VIVO

Science.gov (United States)

XU, HE N.; FENG, MIN; MOON, LILY; DOLLOFF, NATHAN; EL-DEIRY, WAFIK; LI, LIN Z.

2015-01-01

The mitochondrial redox state and its heterogeneity of colon cancer at tissue level have not been previously reported. Nor has how p53 regulates mitochondrial respiration been measured at (deep) tissue level, presumably due to the unavailability of the technology that has sufficient spatial resolution and tissue penetration depth. Our prior work demonstrated that the mitochondrial redox state and its intratumor heterogeneity is associated with cancer aggressiveness in human melanoma and breast cancer in mouse models, with the more metastatic tumors exhibiting localized regions of more oxidized redox state. Using the Chance redox scanner with an in-plane spatial resolution of 200 μm, we imaged the mitochondrial redox state of the wild-type p53 colon tumors (HCT116 p53 wt) and the p53-deleted colon tumors (HCT116 p53−/−) by collecting the fluorescence signals of nicotinamide adenine dinucleotide (NADH) and oxidized flavoproteins [Fp, including flavin adenine dinucleotide (FAD)] from the mouse xenografts snap-frozen at low temperature. Our results show that: (1) both tumor lines have significant degree of intratumor heterogeneity of the redox state, typically exhibiting a distinct bi-modal distribution that either correlates with the spatial core–rim pattern or the “hot/cold” oxidation-reduction patches; (2) the p53−/− group is significantly more heterogeneous in the mitochondrial redox state and has a more oxidized tumor core compared to the p53 wt group when the tumor sizes of the two groups are matched; (3) the tumor size dependence of the redox indices (such as Fp and Fp redox ratio) is significant in the p53−/− group with the larger ones being more oxidized and more heterogeneous in their redox state, particularly more oxidized in the tumor central regions; (4) the H&E staining images of tumor sections grossly correlate with the redox images. The present work is the first to reveal at the submillimeter scale the intratumor heterogeneity pattern

Metabolic Dysfunction in Parkinson's Disease: Bioenergetics, Redox Homeostasis and Central Carbon Metabolism.

Science.gov (United States)

Anandhan, Annadurai; Jacome, Maria S; Lei, Shulei; Hernandez-Franco, Pablo; Pappa, Aglaia; Panayiotidis, Mihalis I; Powers, Robert; Franco, Rodrigo

2017-07-01

The loss of dopaminergic neurons in the substantia nigra pars compacta (SNpc) and the accumulation of protein inclusions (Lewy bodies) are the pathological hallmarks of Parkinson's disease (PD). PD is triggered by genetic alterations, environmental/occupational exposures and aging. However, the exact molecular mechanisms linking these PD risk factors to neuronal dysfunction are still unclear. Alterations in redox homeostasis and bioenergetics (energy failure) are thought to be central components of neurodegeneration that contribute to the impairment of important homeostatic processes in dopaminergic cells such as protein quality control mechanisms, neurotransmitter release/metabolism, axonal transport of vesicles and cell survival. Importantly, both bioenergetics and redox homeostasis are coupled to neuro-glial central carbon metabolism. We and others have recently established a link between the alterations in central carbon metabolism induced by PD risk factors, redox homeostasis and bioenergetics and their contribution to the survival/death of dopaminergic cells. In this review, we focus on the link between metabolic dysfunction, energy failure and redox imbalance in PD, making an emphasis in the contribution of central carbon (glucose) metabolism. The evidence summarized here strongly supports the consideration of PD as a disorder of cell metabolism. Copyright © 2017 Elsevier Inc. All rights reserved.

An integrative approach to energy, carbon, and redox metabolism in the cyanobacterium Synechocystis sp. PCC 6803

Energy Technology Data Exchange (ETDEWEB)

Overbeek, Ross; Fonstein, Veronika; Osterman, Andrei; Gerdes, Svetlana; Vassieva, Olga; Zagnitko, Olga; Rodionov, Dmitry

2005-02-15

covering energy, carbon, and redox metabolism in the Synechocystis sp. PCC 6803 and other cyanobacteria has been performed (Specific Aim 4). The main objectives for this year (adjusted to reflect a new, public domain, setting of the Project research team) were: Aim 1. To develop, test, and deploy a new open source system, the SEED, for integrating community-based annotation, and comparative analysis of all publicly available microbial genomes. Develop a comprehensive genomic database by integrating within SEED all publicly available complete and nearly complete genome sequences with special emphasis on genomes of cyanobacteria, phototrophic eukaryotes, and anoxygenic phototrophic bacteria--invaluable for comparative genomic studies of energy and carbon metabolism in Synechocystis sp. PCC 6803. Aim 2. To develop the SEED's biological content in the form of a collection of encoded Subsystems largely covering the conserved cellular machinery in prokaryotes (and central metabolic machinery in eukaryotes). Aim 3. To develop, utilizing core SEED technology, the CyanoSEED--a specialized WEB portal for community-based annotation, and comparative analysis of all publicly available cyanobacterial genomes. Encode the set of additional subsystems representing key metabolic transformations in cyanobacteria and other photoautotrophs. We envisioned this resource as complementary to other public access databases for comparative genomic analysis currently available to the cyanobacterial research community. Aim 4. Perform in-depth analysis of several subsystems covering energy, carbon, and redox metabolism in the Synechocystis sp. PCC 6803 and all other cyanobacteria with available genome sequences. Reveal inconsistencies and gaps in the current knowledge of these subsystems. Use functional and genome context analysis tools in CyanoSEED to predict, whenever possible, candidate genes for inferred functional roles. To disseminate freely these conjectures and predictions by publishing

1,3-Dioxolane, tetrahydrofuran, acetylacetone and dimethyl sulfoxide as solvents for non-aqueous vanadium acetylacetonate redox-flow-batteries

International Nuclear Information System (INIS)

Herr, T.; Noack, J.; Fischer, P.; Tübke, J.

2013-01-01

Highlights: • Four solvents were employed in a non-aqueous redox flow battery system. • Coulombic efficiencies of 85.9–98.5% and energy efficiencies of 26.6–43.6% were achieved. • Discharge power density was enhanced up to 0.080 mW cm −2 . • Solubility of V(acac) 3 was increased to 0.8 M compared to the acetonitrile system. -- Abstract: A non-aqueous vanadium acetylacetonate redox flow battery with different organic solvents and tetrabutylammonium hexafluorophosphate has been investigated. Cyclic voltammograms show three redox couples in 1,3-dioxolane, tetrahydrofuran, acetylacetone and two redox couples in dimethyl sulfoxide. Cell potentials between 2.21 and 2.61 V are measured, depending on the solvent used. Impedance Spectroscopy has been used to determine rate limiting step in the non-aqueous redox flow battery. Experiments in a charge–discharge test cell yielded coulombic and energy efficiencies of 85.9–98.5% and 26.6–43.6%, respectively

A low-frequency MEMS piezoelectric energy harvester with a rectangular hole based on bulk PZT film

Science.gov (United States)

Tian, Yingwei; Li, Guimiao; Yi, Zhiran; Liu, Jingquan; Yang, Bin

2018-06-01

This paper presents a high performance piezoelectric energy harvester (PEH) with a rectangular hole to work at low-frequency. This PEH used thinned bulk PZT film on flexible phosphor bronze, and its structure included piezoelectric layer, supporting layer and proof mass to reduce the resonant frequency of the device. Here, thinned bulk PZT thick film was used as piezoelectric layer due to its high piezoelectric coefficient. A Phosphor bronze was deployed as supporting layer because it had better flexibility compared to silicon and could work under high acceleration ambient with good durability. The maximum open-circuit voltage of the PEH was 15.7 V at low resonant frequency of 34.3 Hz when the input vibration acceleration was 1.5 g (g = 9.81 m/s2). Moreover, the maximum output power, the output power density and the actually current at the same acceleration were 216.66 μW, 1713.58 μW/cm3 and 170 μA, respectively, when the optimal matched resistance of 60 kΩ was connected. The fabricated PEH scavenged the vibration energy of the vacuum compression pump and generated the maximum output voltage of 1.19 V.

Redox Pioneer: Professor Vadim N. Gladyshev.

Science.gov (United States)

Hatfield, Dolph L

2016-07-01

Professor Vadim N. Gladyshev is recognized here as a Redox Pioneer, because he has published an article on antioxidant/redox biology that has been cited more than 1000 times and 29 articles that have been cited more than 100 times. Gladyshev is world renowned for his characterization of the human selenoproteome encoded by 25 genes, identification of the majority of known selenoprotein genes in the three domains of life, and discoveries related to thiol oxidoreductases and mechanisms of redox control. Gladyshev's first faculty position was in the Department of Biochemistry, the University of Nebraska. There, he was a Charles Bessey Professor and Director of the Redox Biology Center. He then moved to the Department of Medicine at Brigham and Women's Hospital, Harvard Medical School, where he is Professor of Medicine and Director of the Center for Redox Medicine. His discoveries in redox biology relate to selenoenzymes, such as methionine sulfoxide reductases and thioredoxin reductases, and various thiol oxidoreductases. He is responsible for the genome-wide identification of catalytic redox-active cysteines and for advancing our understanding of the general use of cysteines by proteins. In addition, Gladyshev has characterized hydrogen peroxide metabolism and signaling and regulation of protein function by methionine-R-sulfoxidation. He has also made important contributions in the areas of aging and lifespan control and pioneered applications of comparative genomics in redox biology, selenium biology, and aging. Gladyshev's discoveries have had a profound impact on redox biology and the role of redox control in health and disease. He is a true Redox Pioneer. Antioxid. Redox Signal. 25, 1-9.

Thermal Coefficient of Redox Potential of Alkali Metals

Science.gov (United States)

Fukuzumi, Yuya; Hinuma, Yoyo; Moritomo, Yutaka

2018-05-01

The thermal coefficient (α) of redox potential (V) is a significant physical quantity that converts the thermal energy into electric energy. In this short note, we carefully determined α of alkali metals (A = Li and Na) against electrolyte solution. The obtained α is much larger than that expected from the specific heat (CpA) of solid A and depends on electrolyte solution. These observations indicate that the solvent has significant effect on α.

Observation of core-level binding energy shifts between (100) surface and bulk atoms of epitaxial CuInSe{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Nelson, A.J. [Colorado School of Mines, Golden, CO (United States); Berry, G.; Rockett, A. [Univ. of Illinois, Urbana-Champaign, IL (United States)] [and others

1997-04-01

Core-level and valence band photoemission from semiconductors has been shown to exhibit binding energy differences between surface atoms and bulk atoms, thus allowing one to unambiguously distinguish between the two atomic positions. Quite clearly, surface atoms experience a potential different from the bulk due to the lower coordination number - a characteristic feature of any surface is the incomplete atomic coordination. Theoretical accounts of this phenomena are well documented in the literature for III-V and II-VI semiconductors. However, surface state energies corresponding to the equilibrium geometry of (100) and (111) surfaces of Cu-based ternary chalcopyrite semiconductors have not been calculated or experimental determined. These compounds are generating great interest for optoelectronic and photovoltaic applications, and are an isoelectronic analog of the II-VI binary compound semiconductors. Surface core-level binding energy shifts depend on the surface cohesive energies, and surface cohesive energies are related to surface structure. For ternary compound semiconductor surfaces, such as CuInSe{sub 2}, one has the possibility of variations in surface stoichiometry. Applying standard thermodynamical calculations which consider the number of individual surface atoms and their respective chemical potentials should allow one to qualitatively determine the magnitude of surface core-level shifts and, consequently, surface state energies.

Opportunities for shear energy scaling in bulk acoustic wave resonators.

Science.gov (United States)

Jose, Sumy; Hueting, Raymond J E

2014-10-01

An important energy loss contribution in bulk acoustic wave resonators is formed by so-called shear waves, which are transversal waves that propagate vertically through the devices with a horizontal motion. In this work, we report for the first time scaling of the shear-confined spots, i.e., spots containing a high concentration of shear wave displacement, controlled by the frame region width at the edge of the resonator. We also demonstrate a novel methodology to arrive at an optimum frame region width for spurious mode suppression and shear wave confinement. This methodology makes use of dispersion curves obtained from finite-element method (FEM) eigenfrequency simulations for arriving at an optimum frame region width. The frame region optimization is demonstrated for solidly mounted resonators employing several shear wave optimized reflector stacks. Finally, the FEM simulation results are compared with measurements for resonators with Ta2O5/ SiO2 stacks showing suppression of the spurious modes.

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. This journal is © the Owner Societies 2011

Energy Level Alignment at Aqueous GaN and ZnO Interfaces

Science.gov (United States)

Hybertsen, Mark S.; Kharche, Neerav; Muckerman, James T.

2014-03-01

Electronic energy level alignment at semiconductor-electrolyte interfaces is fundamental to electrochemical activity. Motivated in particular by the search for new materials that can be more efficient for photocatalysis, we develop a first principles method to calculate this alignment at aqueous interfaces and demonstrate it for the specific case of non-polar GaN and ZnO interfaces with water. In the first step, density functional theory (DFT) based molecular dynamics is used to sample the physical interface structure and to evaluate the electrostatic potential step at the interface. In the second step, the GW approach is used to evaluate the reference electronic energy level separately in the bulk semiconductor (valence band edge energy) and in bulk water (the 1b1 energy level), relative to the internal electrostatic energy reference. Use of the GW approach naturally corrects for errors inherent in the use of Kohn-Sham energy eigenvalues to approximate the electronic excitation energies in each material. With this predicted interface alignment, specific redox levels in water, with potentials known relative to the 1b1 level, can then be compared to the semiconductor band edge positions. Our results will be discussed in the context of experiments in which photoexcited GaN and ZnO drive the hydrogen evolution reaction. Research carried out at Brookhaven National Laboratory under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy.

Nitrogen isotope and trace metal analyses from the Mingolsheim core (Germany): Evidence for redox variations across the Triassic-Jurassic boundary

Science.gov (United States)

Quan, Tracy M.; van de Schootbrugge, Bas; Field, M. Paul; Rosenthal, Yair; Falkowski, Paul G.

2008-06-01

The Triassic-Jurassic (T-J) boundary was one of the largest but least understood mass extinction events in the Phanerozoic. We measured bulk organic nitrogen and carbon isotopes and trace metal concentrations from a core near Mingolsheim (Germany) to infer paleoenvironmental conditions associated with this event. Poorly fossiliferous claystones across the boundary have relatively low δ15N values and low concentrations of redox-sensitive elements, characteristic of an oxic environment with significant terrestrial input. The Early Jurassic features enrichment in δ15N coincident with high redox-sensitive element concentrations, indicating an increase in water column denitrification and decreased oxygen concentrations. These redox state variations are concordant with shifts in abundance and species composition in terrestrial and marine microflora. We propose that the mass extinction at the T-J boundary was caused by a series of events resulting in a long period of stratification, deep-water hypoxia, and denitrification in this region of the Tethys Ocean basin.

Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films

Energy Technology Data Exchange (ETDEWEB)

DeBlase, Catherine R. [Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, United States; Hernández-Burgos, Kenneth [Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, United States; Silberstein, Katharine E. [Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, United States; Rodríguez-Calero, Gabriel G. [Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, United States; Bisbey, Ryan P. [Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, United States; Abruña, Héctor D. [Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, United States; Dichtel, William R. [Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, New York 14853-1301, United States

2015-02-17

Two-dimensional covalent organic frameworks (2D COFs) are ideally suited for organizing redox-active subunits into periodic, permanently porous polymer networks of interest for pseudocapacitive energy storage. Here we describe a method for synthesizing crystalline, oriented thin films of a redox-active 2D COF on Au working electrodes. The thickness of the COF film was controlled by varying the initial monomer concentration. A large percentage (80–99%) of the anthraquinone groups are electrochemically accessible in films thinner than 200 nm, an order of magnitude improvement over the same COF prepared as a randomly oriented microcrystalline powder. As a result, electrodes functionalized with oriented COF films exhibit a 400% increase in capacitance scaled to electrode area as compared to those functionalized with the randomly oriented COF powder. These results demonstrate the promise of redox-active COFs for electrical energy storage and highlight the importance of controlling morphology for optimal performance.

Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films

Energy Technology Data Exchange (ETDEWEB)

DeBlase, Catherine R.; Hernández-Burgos, Kenneth; Silberstein, Katharine E.; Rodríguez-Calero, Gabriel G.; Bisbey, Ryan P.; Abruña, Héctor D.; Dichtel, William R.

2015-03-24

Two-dimensional covalent organic frameworks (2D COFs) are ideally suited for organizing redox-active subunits into periodic, permanently porous polymer networks of interest for pseudocapacitive energy storage. Here we describe a method for synthesizing crystalline, oriented thin films of a redox-active 2D COF on Au working electrodes. The thickness of the COF film was controlled by varying the initial monomer concentration. A large percentage (80–99%) of the anthraquinone groups are electrochemically accessible in films thinner than 200 nm, an order of magnitude improvement over the same COF prepared as a randomly oriented microcrystalline powder. As a result, electrodes functionalized with oriented COF films exhibit a 400% increase in capacitance scaled to electrode area as compared to those functionalized with the randomly oriented COF powder. These results demonstrate the promise of redox-active COFs for electrical energy storage and highlight the importance of controlling morphology for optimal performance.

Effect of redox conditions on pharmaceutical loss during biological wastewater treatment using sequencing batch reactors

DEFF Research Database (Denmark)

Stadler, Lauren B.; Su, Lijuan; Moline, Christopher J.

2015-01-01

We lack a clear understanding of how wastewater treatment plant (WWTP) process parameters, such as redox environment, impact pharmaceutical fate. WWTPs increasingly install more advanced aeration control systems to save energy and achieve better nutrient removal performance. The impact of redox...... under different redox conditions: fully aerobic, anoxic/aerobic, and microaerobic (DO concentration ≈0.3 mg/L). Among the pharmaceuticals that were tracked during this study (atenolol, trimethoprim, sulfamethoxazole, desvenlafaxine, venlafaxine, and phenytoin), overall loss varied between them...... and between redox environments. Losses of atenolol and trimethoprim were highest in the aerobic reactor; sulfamethoxazole loss was highest in the microaerobic reactors; and phenytoin was recalcitrant in all reactors. Transformation products of sulfamethoxazole and desvenlafaxine resulted in the reformation...

Compromised redox homeostasis, altered nitroso-redox balance, and therapeutic possibilities in atrial fibrillation.

Science.gov (United States)

Simon, Jillian N; Ziberna, Klemen; Casadei, Barbara

2016-04-01

Although the initiation, development, and maintenance of atrial fibrillation (AF) have been linked to alterations in myocyte redox state, the field lacks a complete understanding of the impact these changes may have on cellular signalling, atrial electrophysiology, and disease progression. Recent studies demonstrate spatiotemporal changes in reactive oxygen species production shortly after the induction of AF in animal models with an uncoupling of nitric oxide synthase activity ensuing in the presence of long-standing persistent AF, ultimately leading to a major shift in nitroso-redox balance. However, it remains unclear which radical or non-radical species are primarily involved in the underlying mechanisms of AF or which proteins are targeted for redox modification. In most instances, only free radical oxygen species have been assessed; yet evidence from the redox signalling field suggests that non-radical species are more likely to regulate cellular processes. A wider appreciation for the distinction of these species and how both species may be involved in the development and maintenance of AF could impact treatment strategies. In this review, we summarize how redox second-messenger systems are regulated and discuss the recent evidence for alterations in redox regulation in the atrial myocardium in the presence of AF, while identifying some critical missing links. We also examine studies looking at antioxidants for the prevention and treatment of AF and propose alternative redox targets that may serve as superior therapeutic options for the treatment of AF. © The Author 2016. Published by Oxford University Press on behalf of the European Society of Cardiology.

Engineering redox balance through cofactor systems.

Science.gov (United States)

Chen, Xiulai; Li, Shubo; Liu, Liming

2014-06-01

Redox balance plays an important role in the production of enzymes, pharmaceuticals, and chemicals. To meet the demands of industrial production, it is desirable that microbes maintain a maximal carbon flux towards target metabolites with no fluctuations in redox. This requires functional cofactor systems that support dynamic homeostasis between different redox states or functional stability in a given redox state. Redox balance can be achieved by improving the self-balance of a cofactor system, regulating the substrate balance of a cofactor system, and engineering the synthetic balance of a cofactor system. This review summarizes how cofactor systems can be manipulated to improve redox balance in microbes. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

2017-02-13

Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, non-aqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of non-aqueous electrolytes. However, significant technical hurdles exist currently limiting non-aqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we recently reported a non-aqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox material exhibits an ambipolar electrochemical property, and therefore can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry. Moreover, we demonstrated that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC), as cross-validated by electron spin resonance (ESR) measurements. Herein we present a video protocol for the electrochemical evaluation and SOC diagnosis of the PTIO symmetric flow battery. With a detailed description, we experimentally demonstrated the route to achieve such purposes. This protocol aims to spark more interests and insights on the safety and reliability in the field of non-aqueous redox flow batteries.

Brane big bang brought on by a bulk bubble

International Nuclear Information System (INIS)

Gen, Uchida; Ishibashi, Akihiro; Tanaka, Takahiro

2002-01-01

We propose an alternative inflationary universe scenario in the context of Randall-Sundrum braneworld cosmology. In this new scenario the existence of extra dimension(s) plays an essential role. First, the brane universe is initially in the inflationary phase driven by the effective cosmological constant induced by a small mismatch between the vacuum energy in the five-dimensional bulk and the brane tension. This mismatch arises since the bulk is initially in a false vacuum. Then, false vacuum decay occurs, nucleating a true vacuum bubble with negative energy inside the bulk. The nucleated bubble expands in the bulk and consequently hits the brane, causing a hot big-bang brane universe of the Randall-Sundrum type. Here, the termination of the inflationary phase is due to the change of the bulk vacuum energy. The bubble kinetic energy heats up the universe. As a simple realization, we propose a model in which we assume an interaction between the brane and the bubble. We derive the constraints on the model parameters taking into account the following requirements: solving the flatness problem, no force which prohibits the bubble from colliding with the brane, a sufficiently high reheating temperature for the standard nucleosynthesis to work, and the recovery of Newton's law up to 1 mm. We find that a fine-tuning is needed in order to satisfy the first and the second requirements simultaneously, although the other constraints are satisfied in a wide range of the model parameters

Rechargable Lithium-Air Batteries: Investigation of Redox Mediators Using DEMS

DEFF Research Database (Denmark)

Christensen, Mathias Kjærgård; Storm, Mie Møller; Norby, Poul

2016-01-01

material or electrolyte is being decomposed. This is also seen with Thermally reduced Graphene Oxide (TrGO). The graphene based cathode is interesting as it exhibits a high surface area which in turn increases capacity. Using the additive LiI, functioning as a redox mediator, the discharge curve remains...... is observed without the redox mediator [2]. This results in higher energy densities and ideally higher cyclability due to the lower over-potentials. Using DEMS we have investigated the gas evolved in the process to determine the electron to oxygen ratio using both cathode materials mentioned. As has been...

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.

Dissecting Redox Biology Using Fluorescent Protein Sensors.

Science.gov (United States)

Schwarzländer, Markus; Dick, Tobias P; Meyer, Andreas J; Morgan, Bruce

2016-05-01

Fluorescent protein sensors have revitalized the field of redox biology by revolutionizing the study of redox processes in living cells and organisms. Within one decade, a set of fundamental new insights has been gained, driven by the rapid technical development of in vivo redox sensing. Redox-sensitive yellow and green fluorescent protein variants (rxYFP and roGFPs) have been the central players. Although widely used as an established standard tool, important questions remain surrounding their meaningful use in vivo. We review the growing range of thiol redox sensor variants and their application in different cells, tissues, and organisms. We highlight five key findings where in vivo sensing has been instrumental in changing our understanding of redox biology, critically assess the interpretation of in vivo redox data, and discuss technical and biological limitations of current redox sensors and sensing approaches. We explore how novel sensor variants may further add to the current momentum toward a novel mechanistic and integrated understanding of redox biology in vivo. Antioxid. Redox Signal. 24, 680-712.

Redox Buffer Strength

Science.gov (United States)

de Levie, Robert

1999-04-01

The proper functioning of enzymes in bodily fluids requires that the pH be maintained within rather narrow limits. The first line of defense against large pH fluctuations in such fluids is the passive control provided by the presence of pH buffers. The ability of pH buffers to stabilize the pH is indicated by the buffer value b introduced in 1922 by van Slyke. It is equally important for many enzymes that the redox potential is kept within a narrow range. In that case, stability of the potential is most readily achieved with a redox buffer. In this communication we define the redox buffer strength by analogy with acid-base buffer strength.

Manganese and iron geochemistry in sediments underlying the redox-stratified Fayetteville Green Lake

Science.gov (United States)

Herndon, Elizabeth M.; Havig, Jeff R.; Singer, David M.; McCormick, Michael L.; Kump, Lee R.

2018-06-01

Manganese and iron are redox-sensitive elements that yield clues about biogeochemistry and redox conditions both in modern environments and in the geologic past. Here, we investigated Mn and Fe-bearing minerals preserved in basin sediments underlying Fayetteville Green Lake, a redox-stratified lake that serves as a geochemical analogue for Paleoproterozoic oceans. Synchrotron-source microprobe techniques (μXRF, μXANES, and μXRD) and bulk geochemical analyses were used to examine the microscale distribution and speciation of Mn, Fe, and S as a function of depth in the top 48 cm of anoxic lake sediments. Manganese was primarily associated with calcite grains as a manganese-rich carbonate that precipitated in the chemocline of the water column and settled through the euxinic basin to collect in lake sediments. Iron was preserved in framboidal iron sulfides that precipitated in euxinic bottom waters and underwent transformation to pyrite and marcasite in the sediments. Previous studies attribute the formation of manganese-rich carbonates to the diagenetic alteration of manganese oxides deposited in basins underlying oxygenated water. Our study challenges this paradigm by providing evidence that Mn-bearing carbonates form in the water column and accumulate in sediments below anoxic waters. Consequently, manganoan carbonates preserved in the rock record do not necessarily denote the presence of oxygenated bottom waters in ocean basins.

Phenomenology of Bulk Scalar Production at the LHC

CERN Document Server

Beauchemin , Pierre-Hugues; Burgess, Cliff

We examine the sensitivity of the ATLAS detector to extra-dimensional scalars in scenarios having the extra-dimensional Planck scale in the TeV range and n = 2 large extra dimensions. Such scalars appear as partners of the graviton in higher-dimensional supersymmetric theories. Using first the scalar's lowest-dimensional effective couplings to quarks and gluons, we compute the rate of production of a hard jet together with missing energy. We find a nontrivial range of bulk scalar couplings for which ATLAS could observe a signal, and in particular, higher sensitivity to couplings to gluons than to quarks. Bulk scalar emission increases the missing-energy signal by adding to graviton production, and so complicates the inference of the extra-dimensional Planck scale from the observed rate of jet + EmissT . Because bulk scalar differential cross sections resemble those for gravitons, it is unlikely that these can be experimentally distinguished should a missing energy signal be observed. However, given, for examp...

Competing for phosphors under changing redox conditions: biological versus geochemical sinks

Science.gov (United States)

Gross, A.; Pett-Ridge, J.; Silver, W. L.

2016-12-01

Competing for phosphorus under changing redox conditions: biological versus geochemical sinksAvner Gross1, Jennifer Pett-Ridge2 and Whendee L Silver1 University of California Berkeley, Department of Environmental Science, Policy, & Management, Berkeley, CA, USA. Lawrence Livermore National Laboratory, Physical and Life Science Directorate, Livermore, CA, USA. The cycling of phosphorous (P) in highly weathered, humid tropical forest soils is tightly regulated by P sorption dynamics to the surfaces of Fe(III) (hydr)oxides and root and microbial demands for P. Periods of anoxic soil conditions, which are common in humid environments, induce the reduction of Fe (III) to Fe (II) and may release sorbed P into the soil solution. The microbial demand for P is influenced by the C and nutrient composition of their available substrates. Therefore, we hypothesize that soil redox conditions and substrate quality and availability will control the partitioning of P between microbial biomass and the soil mineral phase. The aim of this study was to examine how fluctuations in soil redox conditions and changes in microbial P demand affect the fate of new P that enters the soil solution. To achieve this aim we conducted a series of soil incubation experiments using a wet tropical soil from Puerto Rico (where redox conditions and P availability naturally oscillate) with a single pulse of phosphate (PO4), altering both the microbial activity and redox conditions. To follow the fate the added P, the added phosphate was labeled with 18O. As the exchange of oxygen between phosphate and water only occurs during biological processes, P-18O labeling can be used as an indicator of microbial use. To quantify sizes of the microbial and mineral P pools we used traditional chemical extractions in the bulk scale. We used NanoSIMS isotopic imaging to map the distribution of P-16O and P-18O and co-localization with Fe minerals at the nano scale. Our results show that the amount of the added P fixed

Mesoscale structural characterization within bulk materials by high-energy X-ray microdiffraction

DEFF Research Database (Denmark)

Lienert, U.; Poulsen, H.F.; Kvick, Å.

2001-01-01

A novel diffraction technique for the local three-dimensional characterization within polycrystalline bulk materials is presented. The technique uses high-energy synchrotron radiation (40 keV materials. Focusing broadband optics have been developed...... experimental evidence that a longitudinal resolution down to 10 mum can be obtained. Fundamental materials properties such as the strain/stress state, grain-orientation, -size, and -surface topology can be probed and mapped in three dimensions in favorable cases. Imbedded volumes and interfaces become...... accessible. The technique is nondestructive and allows for in situ studies of samples in complicated environments. A dedicated experimental station has been constructed at the ID11 beamline of the European Synchrotron Radiation Facility. On-line two-dimensional detectors and conical slits have been developed...

Non-volatile memory devices with redox-active diruthenium molecular compound

International Nuclear Information System (INIS)

Pookpanratana, S; Zhu, H; Bittle, E G; Richter, C A; Li, Q; Hacker, C A; Natoli, S N; Ren, T

2016-01-01

Reduction-oxidation (redox) active molecules hold potential for memory devices due to their many unique properties. We report the use of a novel diruthenium-based redox molecule incorporated into a non-volatile Flash-based memory device architecture. The memory capacitor device structure consists of a Pd/Al 2 O 3 /molecule/SiO 2 /Si structure. The bulky ruthenium redox molecule is attached to the surface by using a ‘click’ reaction and the monolayer structure is characterized by x-ray photoelectron spectroscopy to verify the Ru attachment and molecular density. The ‘click’ reaction is particularly advantageous for memory applications because of (1) ease of chemical design and synthesis, and (2) provides an additional spatial barrier between the oxide/silicon to the diruthenium molecule. Ultraviolet photoelectron spectroscopy data identified the energy of the electronic levels of the surface before and after surface modification. The molecular memory devices display an unsaturated charge storage window attributed to the intrinsic properties of the redox-active molecule. Our findings demonstrate the strengths and challenges with integrating molecular layers within solid-state devices, which will influence the future design of molecular memory devices. (paper)

On the bulk viscosity of relativistic matter

International Nuclear Information System (INIS)

Canuto, V.; Hsieh, S.-H.

1978-01-01

An expression for the bulk viscosity coefficient in terms of the trace of the hydrodynamic energy-stress tensor is derived from the Kubo formula. This, along with a field-theoretic model of an interacting system of scalar particles, suggests that at high temperatures the bulk viscosity tends to zero, contrary to the often quoted resuls of Iso, Mori and Namiki. (author)

Bulk to nanostructured vanadium pentaoxide-nanowires (V2O5-NWs) for high energy density supercapacitors

Science.gov (United States)

Ahirrao, Dinesh J.; Mohanapriya., K.; Jha, Neetu

2018-04-01

Vanadium pentoxide (V2O5) has attracted huge attention in field of energy storage including supercapacitor electrodes due to its low cost and layered structure. In this present study, Bulk V2O5 has been prepared by the calcination of ammonium metavanadate followed by the synthesis of V2O5-nanowires (V2O5-NWs) by hydrothermal treatment of bulk V2O5. Obtained V2O5-NWs was further used to fabricate the supercapacitor electrodes. Structure and morphology analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). Energy storage capability of as prepared nanowires was investigated by Galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in aqueous electrolyte (1M H2SO4). High specific capacitantance of about 622 F/g was achieved at 1 A/g. Along with high storage by faradic charge storage mechanism; V2O5-NWs electrodes also possess high stability. It could retain 63% of its initial capacitance even after 1000 GCD cycles. Excellent performance of V2O5-NWs promotes its commercial utilization for the development of high performance supercapacitors.

Metabolic response of Pseudomonas putida during redox biocatalysis in the presence of a second octanol phase.

Science.gov (United States)

Blank, Lars M; Ionidis, Georgios; Ebert, Birgitta E; Bühler, Bruno; Schmid, Andreas

2008-10-01

A key limitation of whole-cell redox biocatalysis for the production of valuable, specifically functionalized products is substrate/product toxicity, which can potentially be overcome by using solvent-tolerant micro-organisms. To investigate the inter-relationship of solvent tolerance and energy-dependent biocatalysis, we established a model system for biocatalysis in the presence of toxic low logP(ow) solvents: recombinant solvent-tolerant Pseudomonas putida DOT-T1E catalyzing the stereospecific epoxidation of styrene in an aqueous/octanol two-liquid phase reaction medium. Using (13)C tracer based metabolic flux analysis, we investigated the central carbon and energy metabolism and quantified the NAD(P)H regeneration rate in the presence of toxic solvents and during redox biocatalysis, which both drastically increased the energy demands of solvent-tolerant P. putida. According to the driven by demand concept, the NAD(P)H regeneration rate was increased up to eightfold by two mechanisms: (a) an increase in glucose uptake rate without secretion of metabolic side products, and (b) reduced biomass formation. However, in the presence of octanol, only approximately 1% of the maximally observed NAD(P)H regeneration rate could be exploited for styrene epoxidation, of which the rate was more than threefold lower compared with operation with a non-toxic solvent. This points to a high energy and redox cofactor demand for cell maintenance, which limits redox biocatalysis in the presence of octanol. An estimated upper bound for the NAD(P)H regeneration rate available for biocatalysis suggests that cofactor availability does not limit redox biocatalysis under optimized conditions, for example, in the absence of toxic solvent, and illustrates the high metabolic capacity of solvent-tolerant P. putida. This study shows that solvent-tolerant P. putida have the remarkable ability to compensate for high energy demands by boosting their energy metabolism to levels up to an order of

Redox Flow Batteries, Hydrogen and Distributed Storage.

Science.gov (United States)

Dennison, C R; Vrubel, Heron; Amstutz, Véronique; Peljo, Pekka; Toghill, Kathryn E; Girault, Hubert H

2015-01-01

Social, economic, and political pressures are causing a shift in the global energy mix, with a preference toward renewable energy sources. In order to realize widespread implementation of these resources, large-scale storage of renewable energy is needed. Among the proposed energy storage technologies, redox flow batteries offer many unique advantages. The primary limitation of these systems, however, is their limited energy density which necessitates very large installations. In order to enhance the energy storage capacity of these systems, we have developed a unique dual-circuit architecture which enables two levels of energy storage; first in the conventional electrolyte, and then through the formation of hydrogen. Moreover, we have begun a pilot-scale demonstration project to investigate the scalability and technical readiness of this approach. This combination of conventional energy storage and hydrogen production is well aligned with the current trajectory of modern energy and mobility infrastructure. The combination of these two means of energy storage enables the possibility of an energy economy dominated by renewable resources.

High energy power-law tail in X-ray binaries and bulk Comptonization due to an outflow from a disk

Science.gov (United States)

Kumar, Nagendra

2018-02-01

We study the high energy power-law tail emission of X-ray binaries (XRBs) by a bulk Comptonization process which is usually observed in the very high soft (VHS) state of black hole (BH) XRBs and the high soft (HS) state of the neutron star (NS) and BH XRBs. Earlier, to generate the power-law tail in bulk Comptonization framework, a free-fall converging flow into BH or NS had been considered as a bulk region. In this work, for a bulk region we consider mainly an outflow geometry from the accretion disk which is bounded by a torus surrounding the compact object. We have two choices for an outflow geometry: (i) collimated flow and (ii) conical flow of opening angle θ _b and the axis is perpendicular to the disk. We also consider an azimuthal velocity of the torus fluids as a bulk motion where the fluids are rotating around the compact object (a torus flow). We find that the power-law tail can be generated in a torus flow having large optical depth and bulk speed (>0.75 c), and in conical flow with θ _b > ˜ 30° for a low value of Comptonizing medium temperature. Particularly, in conical flow the low opening angle is more favourable to generate the power-law tail in both the HS state and the VHS state. We notice that when the outflow is collimated, then the emergent spectrum does not have power-law component for a low Comptonizing medium temperature.

Fundamentally Addressing Bromine Storage through Reversible Solid-State Confinement in Porous Carbon Electrodes: Design of a High-Performance Dual-Redox Electrochemical Capacitor.

Science.gov (United States)

Yoo, Seung Joon; Evanko, Brian; Wang, Xingfeng; Romelczyk, Monica; Taylor, Aidan; Ji, Xiulei; Boettcher, Shannon W; Stucky, Galen D

2017-07-26

Research in electric double-layer capacitors (EDLCs) and rechargeable batteries is converging to target systems that have battery-level energy density and capacitor-level cycling stability and power density. This research direction has been facilitated by the use of redox-active electrolytes that add faradaic charge storage to increase energy density of the EDLCs. Aqueous redox-enhanced electrochemical capacitors (redox ECs) have, however, performed poorly due to cross-diffusion of soluble redox couples, reduced cycle life, and low operating voltages. In this manuscript, we propose that these challenges can be simultaneously met by mechanistically designing a liquid-to-solid phase transition of oxidized catholyte (or reduced anolyte) with confinement in the pores of electrodes. Here we demonstrate the realization of this approach with the use of bromide catholyte and tetrabutylammonium cation that induces reversible solid-state complexation of Br 2 /Br 3 - . This mechanism solves the inherent cross-diffusion issue of redox ECs and has the added benefit of greatly stabilizing the reactive bromine generated during charging. Based on this new mechanistic insight on the utilization of solid-state bromine storage in redox ECs, we developed a dual-redox EC consisting of a bromide catholyte and an ethyl viologen anolyte with the addition of tetrabutylammonium bromide. In comparison to aqueous and organic electric double-layer capacitors, this system enhances energy by factors of ca. 11 and 3.5, respectively, with a specific energy of ∼64 W·h/kg at 1 A/g, a maximum power density >3 kW/kg, and cycling stability over 7000 cycles.

The redox reaction kinetics of Sinai ore for chemical looping combustion applications

International Nuclear Information System (INIS)

Ksepko, Ewelina; Babiński, Piotr; Nalbandian, Lori

2017-01-01

Highlights: • Redox reaction kinetics of Fe-Mn-rich Sinai ore was determined by TGA. • The most suitable model for reduction was D3, while R3 for oxidation. • Activation energies 35.3 and 16.70 kJ/mole were determined for reduction and oxidation. • Repetitive redox reactions favor the formation of spinel phases in Sinai ore. • Multiple redox cycles induce formation of extensive porosity of the particles. - Abstract: The objective of this work was to study the use of Sinai ore, a Fe–Mn-based ore from Egypt, as a low-cost oxygen carrier (OC) in Chemical Looping Combustion (CLC). The Sinai ore was selected because it possesses relatively high amounts of iron and manganese oxides. Furthermore, those oxides have low cost, very favorable environmental and thermodynamic properties for the CLC process. The performance of the Sinai ore as an OC in CLC was compared to that of ilmenite (Norway Tellnes mine), the most extensively studied naturally occurring Fe-based mineral. The kinetics of the reduction and oxidation reactions with the two minerals were studied using a thermogravimetric analyzer (TGA). Experiments were conducted under isothermal conditions, with multiple redox cycles, at temperatures between 750 and 950 °C. For the reduction and oxidation reactions, different concentrations of CH_4 (10–25 vol.%) and O_2 (5–20 vol.%) were applied, respectively. The kinetic parameters, such as the activation energy (E_a), pre-exponential factor (A_0), and reaction order (n), were determined for the redox reactions. Furthermore, models of the redox reactions were selected by means of a model-fitting method. For the Sinai ore, the D3 model (3-dimensional diffusion) was suitable for modeling reduction reaction kinetics. The calculated E_a was 35.3 kJ/mole, and the reaction order was determined to be approximately 0.76. The best fit for the oxidation reaction was obtained for the R3 model (shrinking core). The oxidation (regeneration) reaction E_a was equal to 16

Electronic properties of Mn-phthalocyanine–C60 bulk heterojunctions: Combining photoemission and electron energy-loss spectroscopy

International Nuclear Information System (INIS)

Roth, Friedrich; Herzig, Melanie; Knupfer, Martin; Lupulescu, Cosmin; Darlatt, Erik; Gottwald, Alexander; Eberhardt, Wolfgang

2015-01-01

The electronic properties of co-evaporated mixtures (blends) of manganese phthalocyanine and the fullerene C 60 (MnPc:C 60 ) have been studied as a function of the concentration of the two constituents using two supplementary electron spectroscopic methods, photoemission spectroscopy (PES) and electron energy-loss spectroscopy (EELS) in transmission. Our PES measurements provide a detailed picture of the electronic structure measured with different excitation energies as well as different mixing ratios between MnPc and C 60 . Besides a relative energy shift, the occupied electronic states of the two materials remain essentially unchanged. The observed energy level alignment is different compared to that of the related CuPc:C 60 bulk heterojunction. Moreover, the results from our EELS investigations show that, despite the rather small interface interaction, the MnPc related electronic excitation spectrum changes significantly by admixing C 60 to MnPc thin films

High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries.

Science.gov (United States)

Hendriks, Koen H; Robinson, Sophia G; Braten, Miles N; Sevov, Christo S; Helms, Brett A; Sigman, Matthew S; Minteer, Shelley D; Sanford, Melanie S

2018-02-28

Nonaqueous redox flow batteries (NRFBs) represent an attractive technology for energy storage from intermittent renewable sources. In these batteries, electrical energy is stored in and extracted from electrolyte solutions of redox-active molecules (termed catholytes and anolytes) that are passed through an electrochemical flow cell. To avoid battery self-discharge, the anolyte and catholyte solutions must be separated by a membrane in the flow cell. This membrane prevents crossover of the redox active molecules, while simultaneously allowing facile transport of charge-balancing ions. A key unmet challenge for the field is the design of redox-active molecule/membrane pairs that enable effective electrolyte separation while maintaining optimal battery properties. Herein, we demonstrate the development of oligomeric catholytes based on tris(dialkylamino)cyclopropenium (CP) salts that are specifically tailored for pairing with size-exclusion membranes composed of polymers of intrinsic microporosity (PIMs). Systematic studies were conducted to evaluate the impact of oligomer size/structure on properties that are crucial for flow battery performance, including cycling stability, charge capacity, solubility, electron transfer kinetics, and crossover rates. These studies have led to the identification of a CP-derived tetramer in which these properties are all comparable, or significantly improved, relative to the monomeric counterpart. Finally, a proof-of-concept flow battery is demonstrated by pairing this tetrameric catholyte with a PIM membrane. After 6 days of cycling, no crossover is detected, demonstrating the promise of this approach. These studies provide a template for the future design of other redox-active oligomers for this application.

Fe-phyllosilicate redox cycling organisms from a redox transition zone in Hanford 300 Area sediments

Directory of Open Access Journals (Sweden)

Jason eBenzine

2013-12-01

Full Text Available Microorganisms capable of reducing or oxidizing structural iron (Fe in Fe-bearing phyllosilicate minerals were enriched and isolated from a subsurface redox transition zone at the Hanford 300 Area site in eastern Washington, USA. Both conventional and in situ i-chip enrichment strategies were employed. One Fe(III-reducing Geobacter (G. bremensis strain R1, Deltaproteobacteria and six Fe(II phyllosilicate-oxidizing isolates from the Alphaproteobacteria (Bradyrhizobium japonicum strains 22, is5, and in8p8, Betaproteobacteria (Cupriavidus necator strain A5-1, Dechloromonas agitata strain is5, and Actinobacteria (Nocardioides sp. strain in31 were recovered. The G. bremensis isolate grew by oxidizing acetate with the oxidized form of NAu-2 smectite as the electron acceptor. The Fe(II-oxidizers grew by oxidation of chemically reduced smectite as the energy source with nitrate as the electron acceptor. The Bradyrhizobium isolates could also carry out aerobic oxidation of biotite. This is the first report of the recovery of a Fe(II-oxidizing Nocardioides, and to date only one other Fe(II-oxidizing Bradyrhizobium is known. The 16S rRNA gene sequences of the isolates were similar to ones found in clone libraries from Hanford 300 sediments and groundwater, suggesting that such organisms may be present and active in situ. Whole genome sequencing of the isolates is underway, the results of which will enable comparative genomic analysis of mechanisms of extracellular phyllosilicate Fe redox metabolism, and facilitate development of techniques to detect the presence and expression of genes associated with microbial phyllosilicate Fe redox cycling in sediments.

A 3.5 V lithium-iodine hybrid redox battery with vertically aligned carbon nanotube current collector.

Science.gov (United States)

Zhao, Yu; Hong, Misun; Bonnet Mercier, Nadège; Yu, Guihua; Choi, Hee Cheul; Byon, Hye Ryung

2014-02-12

A lithium-iodine (Li-I2) cell using the triiodide/iodide (I3(-)/I(-)) redox couple in an aqueous cathode has superior gravimetric and volumetric energy densities (∼ 330 W h kg(-1) and ∼ 650 W h L(-1), respectively, from saturated I2 in an aqueous cathode) to the reported aqueous Li-ion batteries and aqueous cathode-type batteries, which provides an opportunity to construct cost-effective and high-performance energy storage. To apply this I3(-)/I(-) aqueous cathode for a portable and compact 3.5 V battery, unlike for grid-scale storage as general target of redox flow batteries, we use a three-dimensional and millimeter thick carbon nanotube current collector for the I3(-)/I(-) redox reaction, which can shorten the diffusion length of the redox couple and provide rapid electron transport. These endeavors allow the Li-I2 battery to enlarge its specific capacity, cycling retention, and maintain a stable potential, thereby demonstrating a promising candidate for an environmentally benign and reusable portable battery.

Identification of redox-sensitive cysteines in the arabidopsis proteome using OxiTRAQ, a quantitative redox proteomics method

KAUST Repository

Liu, Pei

2014-01-28

Cellular redox status plays a key role in mediating various physiological and developmental processes often through modulating activities of redox-sensitive proteins. Various stresses trigger over-production of reactive oxygen/nitrogen species which lead to oxidative modifications of redox-sensitive proteins. Identification and characterization of redox-sensitive proteins are important steps toward understanding molecular mechanisms of stress responses. Here, we report a high-throughput quantitative proteomic approach termed OxiTRAQ for identifying proteins whose thiols undergo reversible oxidative modifications in Arabidopsis cells subjected to oxidative stress. In this approach, a biotinylated thiol-reactive reagent is used for differential labeling of reduced and oxidized thiols. The biotin-tagged peptides are affinity purified, labeled with iTRAQ reagents, and analyzed using a paralleled HCD-CID fragmentation mode in an LTQ-Orbitrap. With this approach, we identified 195 cysteine-containing peptides from 179 proteins whose thiols underwent oxidative modifications in Arabidopsis cells following the treatment with hydrogen peroxide. A majority of those redox-sensitive proteins, including several transcription factors, were not identified by previous redox proteomics studies. This approach allows identification of the specific redox-regulated cysteine residues, and offers an effective tool for elucidation of redox proteomes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of bulk Micromegas with different amplification gaps

Energy Technology Data Exchange (ETDEWEB)

Bhattacharya, Purba, E-mail: purba.bhattacharya@saha.ac.in [Applied Nuclear Physics Division, Saha Institute of Nuclear Physics, Kolkata 700064 (India); Bhattacharya, Sudeb [Emeritus Scientist (CSIR), Applied Nuclear Physics Division, Saha Institute of Nuclear Physics, Kolkata 700064 (India); Majumdar, Nayana; Mukhopadhyay, Supratik; Sarkar, Sandip [Applied Nuclear Physics Division, Saha Institute of Nuclear Physics, Kolkata 700064 (India); Colas, Paul; Attie, David [DSM/IRFU, CEA/Saclay, F-91191 Gif-sur-Yvette CEDEX (France)

2013-12-21

The bulk Micromegas detector is considered to be a promising candidate for building TPCs for several future experiments including the projected linear collider. The standard bulk with a spacing of 128μm has already established itself as a good choice for its performances in terms of gas gain uniformity, energy and space point resolution, and its capability to efficiently pave large readout surfaces with minimum dead zone. The present work involves the comparison of this standard bulk with a relatively less used bulk Micromegas detector having a larger amplification gap of 192μm. Detector gain, energy resolution and electron transparency of these Micromegas have been measured under different conditions in various Argon-based gas mixtures to evaluate their performance. These measured characteristics have also been compared in detail to numerical simulations using the Garfield framework that combines packages such as neBEM, Magboltz and Heed. Further, we have carried out another numerical study to determine the effect of dielectric spacers on different detector features. A comprehensive comparison of the two detectors has been presented and analyzed in this work. -- Highlights: •We present a comparative study between bulk Micromegas having different amplification gaps. •Various detector characteristics such as gain, electron transparency, energy resolution have been measured experimentally. •Successful comparisons of these measured data with the simulation results indicate that the device physics is quite well understood. •A numerical study to determine the effect of dielectric spacers on different detect or features has been carried out.

The roles of anion and solvent transport during the redox switching process at a poly(butyl viologen) film studied by an EQCM

Energy Technology Data Exchange (ETDEWEB)

Hsu, Chih-Yu.; Liao, Chun-Hao [Department of Chemical Engineering, National Taiwan University, Taipei 10617 (China); Ho, Kuo-Chuan [Department of Chemical Engineering, National Taiwan University, Taipei 10617 (China); Institute of Polymer Science and Engineering, National Taiwan University, Taipei 10617 (China)

2008-02-15

In this study, three electrolytes (KCl, LiCl, and KNO{sub 3}, each at 0.5 M in aqueous solution) were chosen to study the ion and solvent effect on the redox performance of poly(butyl viologen) (PBV) thin-films between its di-cation and radical-cation state, which is referred as its first redox couple. Before considering the role of ionic transport on the redox process, the exchange between ferrocyanide and anion should be completed. Since the deposition solution of PBV contains potassium ferrocyanide, the residual ferrocyanides inside the films would be exchanged by smaller anions from the bulk solution during the redox reaction of PBV. From cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) results, the exchange was almost complete around 50 cycles when scanning the potential within its first redox range. After completion of the exchange process, the transfer would reach a steady state. At 50 cycles, the EQCM results suggested that the transport involves anions and water only for both being extracted upon reduction and being inserted upon oxidation. Therefore, we could obtain the molar fluxes of Cl{sup -}, NO{sub 3}{sup -}, and water. Besides, the average numbers of accompanying water were calculated to be about 24.8 per Cl{sup -} and 14.2 per NO{sub 3}{sup -} upon redox switching process. The instantaneous water to anion molar ratios at any potential were also obtained for Cl{sup -} and NO{sub 3}{sup -}. (author)

Redox Signaling Mediated by Thioredoxin and Glutathione Systems in the Central Nervous System.

Science.gov (United States)

Ren, Xiaoyuan; Zou, Lili; Zhang, Xu; Branco, Vasco; Wang, Jun; Carvalho, Cristina; Holmgren, Arne; Lu, Jun

2017-11-01

The thioredoxin (Trx) and glutathione (GSH) systems play important roles in maintaining the redox balance in the brain, a tissue that is prone to oxidative stress due to its high-energy demand. These two disulfide reductase systems are active in various areas of the brain and are considered to be critical antioxidant systems in the central nervous system (CNS). Various neuronal disorders have been characterized to have imbalanced redox homeostasis. Recent Advances: In addition to their detrimental effects, recent studies have highlighted that reactive oxygen species/reactive nitrogen species (ROS/RNS) act as critical signaling molecules by modifying thiols in proteins. The Trx and GSH systems, which reversibly regulate thiol modifications, regulate redox signaling involved in various biological events in the CNS. In this review, we focus on the following: (i) how ROS/RNS are produced and mediate signaling in CNS; (ii) how Trx and GSH systems regulate redox signaling by catalyzing reversible thiol modifications; (iii) how dysfunction of the Trx and GSH systems causes alterations of cellular redox signaling in human neuronal diseases; and (iv) the effects of certain small molecules that target thiol-based signaling pathways in the CNS. Further study on the roles of thiol-dependent redox systems in the CNS will improve our understanding of the pathogenesis of many human neuronal disorders and also help to develop novel protective and therapeutic strategies against neuronal diseases. Antioxid. Redox Signal. 27, 989-1010.

Analysis of changes in energy and redox states in HepG2 hepatoma and C6 glioma cells upon exposure to cadmium

International Nuclear Information System (INIS)

Yang, M.S.; Yu, L.C.; Gupta, R.C.

2004-01-01

The energy and redox states of the HepG2 hepatoma and the C6 glioma cells were studied by quantifying the levels of ATP, ADP, AMP, GSH, and GSSG. These values were used to calculate the energy charge potential (ECP = [ATP + 0.5ADP]/TAN), total adenosine nucleotides (TAN = ATP + ADP + AMP), total glutathione (TG = [GSH + GSSG]/TAN), and the redox state (GSH/GSSG ratio). For comparison between cell types, the level of each energy metabolite (ATP, ADP, and AMP) was normalized against TAN of the respective cell. The results showed that ATP:ADP:AMP ratio was 0.76:0.11:0.13 for the HepG2 cells and 0.80:0.11:0.09 for the C6 glioma cells. ECP was 0.81 ± 0.01 and 0.85 ± 0.01 for the HepG2 and the C6 glioma cells, respectively. GSH/GSSG ratio was 2.66 ± 0.16 and 3.63 ± 0.48 for HepG2 and C6 glioma cells, respectively. TG was 3.2 ± 0.54 for the HepG2 cells and 2.43 ± 0.18 for the C6 glioma cells, indicating that the level of total glutathione is more than two to three times higher than the total energy metabolites in these cell lines. Following a 3-h incubation in medium containing different concentrations of Cd, there was a dose-dependent decrease in cell viability. The 3-h LC 50 for the HepG2 cells was 0.5 mM and that for the C6 glioma cells was 0.4 mM. Cellular TAN decreased with a decrease in cell viability. Upon careful analysis of the energy state, there was a significant increase in relative amount of ATP and decrease in ADP and AMP in both cells as Cd concentration increased from 0 to 0.1, 0.2, and 0.6 mM. However, ECP in both cell lines increased, which indicated that the level of high energy phosphate was adequate. There was also a significant increase in TG and a significant decrease in GSH/GSSG in the C6 glioma cells when cells were exposed to as low as 0.1 mM Cd, which suggested that the cellular redox state was compromised. The HepG2 cells, on the other hand, showed no significant change in both TG and GSH/GSSG level until Cd concentration reached 0.6 m

Computational design of molecules for an all-quinone redox flow battery.

Science.gov (United States)

Er, Süleyman; Suh, Changwon; Marshak, Michael P; Aspuru-Guzik, Alán

2015-02-01

Inspired by the electron transfer properties of quinones in biological systems, we recently showed that quinones are also very promising electroactive materials for stationary energy storage applications. Due to the practically infinite chemical space of organic molecules, the discovery of additional quinones or other redox-active organic molecules for energy storage applications is an open field of inquiry. Here, we introduce a high-throughput computational screening approach that we applied to an accelerated study of a total of 1710 quinone (Q) and hydroquinone (QH 2 ) ( i.e. , two-electron two-proton) redox couples. We identified the promising candidates for both the negative and positive sides of organic-based aqueous flow batteries, thus enabling an all-quinone battery. To further aid the development of additional interesting electroactive small molecules we also provide emerging quantitative structure-property relationships.

Effect of energy equation in one control-volume bulk-flow model for the prediction of labyrinth seal dynamic coefficients

Science.gov (United States)

Cangioli, Filippo; Pennacchi, Paolo; Vannini, Giuseppe; Ciuchicchi, Lorenzo

2018-01-01

The influence of sealing components on the rotordynamic stability of turbomachinery has become a key topic because the oil and gas market is increasingly demanding high rotational speeds and high efficiency. This leads the turbomachinery manufacturers to design higher flexibility ratios and to reduce the clearance of the seals. Accurate prediction of the effective damping of seals is critical to avoid instability problems; in recent years, "negative-swirl" swirl brakes have been used to reverse the circumferential direction of the inlet flow, which changes the sign of the cross-coupled stiffness coefficients and generates stabilizing forces. Experimental tests for a teeth-on-stator labyrinth seal were performed by manufacturers with positive and negative pre-swirl values to investigate the pre-swirl effect on the cross-coupled stiffness coefficient. Those results are used as a benchmark in this paper. To analyse the rotor-fluid interaction in the seals, the bulk-flow numeric approach is more time efficient than computational fluid dynamics (CFD). Although the accuracy of the coefficients prediction in bulk-flow models is satisfactory for liquid phase application, the accuracy of the results strongly depends on the operating conditions in the case of the gas phase. In this paper, the authors propose an improvement in the state-of-the-art bulk-flow model by introducing the effect of the energy equation in the zeroth-order solution to better characterize real gas properties due to the enthalpy variation along the seal cavities. The consideration of the energy equation allows for a better estimation of the coefficients in the case of a negative pre-swirl ratio, therefore, it extend the prediction fidelity over a wide range of operating conditions. The numeric results are also compared to the state-of-the-art bulk-flow model, which highlights the improvement in the model.

Redox reaction studies by nanosecond pulse radiolysis

International Nuclear Information System (INIS)

Moorthy, P.N.

1979-01-01

Free radicals are formed as intermediates in many chemical and biochemical reactions. An important type of reaction which they can undergo is a one electron or redox process. The direction and rate of such electron transfer reactions is governed by the relative redox potentials of the participating species. Because of the generally short lived nature of free radicals, evaluation of their redox potentials poses a number of problems. Two techniques are described for the experimental determination of the redox potentials of short lived species generated by either a nanosecond electron pulse or laser flash. In the first method, redox titration of the short lived species with stable molecules of known redox potential is carried out, employing the technique of fast kinetic spectrophotometry. Conversely, by the same method it is also possible to evaluate the one electron redox potentials of stable molecules by redox titration with free radicals of known redox potential produced as above. In the second method, electrochemical reduction or oxidation of the short lived species at an appropriate electrode (generally a mercury drop) is carried out at different fixed potentials, and the redox potential evaluated from the current-potential curves (polarograms). Full description of the experimental set up and theoretical considerations for interpretation of the raw data are given. The relative merits of the two methods and their practical applicability are discussed. (auth.)

Redox Conditions and Related Color Change in Eastern Equatorial Pacific Sediments: IODP Site U1334

Science.gov (United States)

Kordesch, W. E.; Gussone, N. C.; Hathorne, E. C.; Kimoto, K.; Delaney, M. L.

2011-12-01

This study was prompted by a 65 m thick brown-green color change in deep-sea sediments of IODP Site U1334 (0-38 Ma, 4799 m water depth) that corresponds to its equatorial crossing (caused by the Northward movement of the pacific plate). Green sediment is a visual indicator of reducing conditions in sediment due to enhanced organic matter deposition and burial. Here we use geochemical redox indicators to characterize the effect of equatorial upwelling on bottom water. The modern redox signal is captured in porewater profiles (nitrate, manganese, iron, sulfate) while trace metal Enrichment Factors (EF) in bulk sediment (manganese, uranium, molybdenum, rhenium) normalized to the detrital component (titanium) record redox state at burial. To measure export productivity we also measure biogenic barium. Porewater profiles reveal suboxic diagenesis; profiles follow the expected sequence of nitrate, manganese oxide, and iron oxide reduction with increasing depth. Constant sulfate (~28 μM) implies anoxia has not occurred. Bulk sediment Mn EF are enriched (EF > 1) throughout the record (Mn EF = 15-200) while U and Mo enrichment corresponds to green color and equatorial proximity (U EF = 4-19; Mo EF = 0-7). Constant Mn enrichment implies continuous oxygenation. Uranium and Mo enrichment near the equator represents suboxic conditions also seen in the porewater. Low Re concentrations (below detection) provide additional evidence against anoxia. A comparison of Mn EF from total digestions to samples treated with an additional reductive cleaning step distinguishes between Mn-oxides and Mn-carbonates, indicating oxygenated and reducing conditions respectively. Mn-carbonate occurrence agrees with U and Mo EF; conditions were more reducing near the equator. Bio-Ba shows significant variability over this interval (22-99 mmol g-1). Our geochemical results indicate that bottom waters became suboxic at the equator as a result of equatorial upwelling-influenced increases in organic

A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized β-polytype porous silicon carbide electrodes.

Science.gov (United States)

Kim, Myeongjin; Yoo, Jeeyoung; Kim, Jooheon

2017-05-23

A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo 2 O 4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo 2 O 4 ) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g -1 at a scan rate of 5 mV s -1 in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe 3 O 4 nanoparticles and SiCF (SiCF/Fe 3 O 4 ) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g -1 at a scan rate of 5 mV s -1 . Therefore, by pairing the SiCF/MgCo 2 O 4 positive electrode and the SiCF/Fe 3 O 4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g -1 at a scan rate of 5 mV s -1 ) and energy density (maximum energy density of 72.79 Wh kg -1 at a power density of 727.96 W kg -1 ).

A study of the Fe(III)/Fe(II)-triethanolamine complex redox couple for redox flow battery application

International Nuclear Information System (INIS)

Wen, Y.H.; Zhang, H.M.; Qian, P.; Zhou, H.T.; Zhao, P.; Yi, B.L.; Yang, Y.S.

2006-01-01

The electrochemical behavior of the Fe(III)/Fe(II)-triethanolamine(TEA) complex redox couple in alkaline medium and influence of the concentration of TEA were investigated. A change of the concentration of TEA mainly produces the following two results. (1) With an increase of the concentration of TEA, the solubility of the Fe(III)-TEA can be increased to 0.6 M, and the solubility of the Fe(II)-TEA is up to 0.4 M. (2) In high concentration of TEA with the ratio of TEA to NaOH ranging from 1 to 6, side reaction peaks on the cathodic main reaction of the Fe(III)-TEA complex at low scan rate can be minimized. The electrode process of Fe(III)-TEA/Fe(II)-TEA is electrochemically reversible with higher reaction rate constant than the uncomplexed species. Constant current charge-discharge shows that applying anodic active materials of relatively high concentrations facilitates the improvement of cell performance. The open-circuit voltage of the Fe-TEA/Br 2 cell with the Fe(III)-TEA of 0.4 M, after full charging, is nearly 2.0 V and is about 32% higher than that of the all-vanadium batteries, together with the energy efficiency of approximately 70%. The preliminary exploration shows that the Fe(III)-TEA/Fe(II)-TEA couple is electrochemically promising as negative redox couple for redox flow battery (RFB) application

Redox flow batteries based on supporting solutions containing chloride

Science.gov (United States)

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.

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

2017-11-14

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.

Imaging dynamic redox processes with genetically encoded probes.

Science.gov (United States)

Ezeriņa, Daria; Morgan, Bruce; Dick, Tobias P

2014-08-01

Redox signalling plays an important role in many aspects of physiology, including that of the cardiovascular system. Perturbed redox regulation has been associated with numerous pathological conditions; nevertheless, the causal relationships between redox changes and pathology often remain unclear. Redox signalling involves the production of specific redox species at specific times in specific locations. However, until recently, the study of these processes has been impeded by a lack of appropriate tools and methodologies that afford the necessary redox species specificity and spatiotemporal resolution. Recently developed genetically encoded fluorescent redox probes now allow dynamic real-time measurements, of defined redox species, with subcellular compartment resolution, in intact living cells. Here we discuss the available genetically encoded redox probes in terms of their sensitivity and specificity and highlight where uncertainties or controversies currently exist. Furthermore, we outline major goals for future probe development and describe how progress in imaging methodologies will improve our ability to employ genetically encoded redox probes in a wide range of situations. This article is part of a special issue entitled "Redox Signalling in the Cardiovascular System." Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis of Bulk Superconducting Magnesium Diboride

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Margie Olbinado

2002-06-01

Full Text Available Bulk polycrystalline superconducting magnesium diboride, MgB2, samples were successfully prepared via a one-step sintering program at 750°C, in pre Argon with a pressure of 1atm. Both electrical resistivity and magnetic susceptibility measurements confirmed the superconductivity of the material at 39K, with a transition width of 5K. The polycrystalline nature, granular morphology, and composition of the sintered bulk material were confirmed using X-ray diffractometry (XRD, scanning electron microscopy (SEM, and energy dispersive X-ray analysis (EDX.

Direct Solar Charging of an Organic-Inorganic, Stable, and Aqueous Alkaline Redox Flow Battery with a Hematite Photoanode.

Science.gov (United States)

Wedege, Kristina; Azevedo, João; Khataee, Amirreza; Bentien, Anders; Mendes, Adélio

2016-06-13

The intermittent nature of the sunlight and its increasing contribution to electricity generation is fostering the energy storage research. Direct solar charging of an auspicious type of redox flow battery could make solar energy directly and efficiently dispatchable. The first solar aqueous alkaline redox flow battery using low cost and environmentally safe materials is demonstrated. The electrolytes consist of the redox couples ferrocyanide and anthraquinone-2,7-disulphonate in sodium hydroxide solution, yielding a standard cell potential of 0.74 V. Photovoltage enhancement strategies are demonstrated for the ferrocyanide-hematite junction by employing an annealing treatment and growing a layer of a conductive polyaniline polymer on the electrode surface, which decreases electron-hole recombination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regulatory redox state in tree seeds

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Ewelina Ratajczak

2017-12-01

Full Text Available Peroxiredoxins (Prx are important regulators of the redox status of tree seeds during maturation and long-term storage. Thioredoxins (Trx are redox transmitters and thereby regulate Prx activity. Current research is focused on the association of Trx with Prx in tree seeds differing in the tolerance to desiccation. The results will allow for better understanding the regulation of the redox status in orthodox, recalcitrant, and intermediate seeds. The findings will also elucidate the role of the redox status during the loss of viability of sensitive seeds during drying and long-term storage.

Tuning of redox regulatory mechanisms, reactive oxygen species and redox homeostasis under salinity stress

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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.

Integrating a redox-coupled dye-sensitized photoelectrode into a lithium-oxygen battery for photoassisted charging.

Science.gov (United States)

Yu, Mingzhe; Ren, Xiaodi; Ma, Lu; Wu, Yiying

2014-10-03

With a high theoretical specific energy, the non-aqueous rechargeable lithium-oxygen battery is a promising next-generation energy storage technique. However, the large charging overpotential remains a challenge due to the difficulty in electrochemically oxidizing the insulating lithium peroxide. Recently, a redox shuttle has been introduced into the electrolyte to chemically oxidize lithium peroxide. Here, we report the use of a triiodide/iodide redox shuttle to couple a built-in dye-sensitized titanium dioxide photoelectrode with the oxygen electrode for the photoassisted charging of a lithium-oxygen battery. On charging under illumination, triiodide ions are generated on the photoelectrode, and subsequently oxidize lithium peroxide. Due to the contribution of the photovoltage, the charging overpotential is greatly reduced. The use of a redox shuttle to couple a photoelectrode and an oxygen electrode offers a unique strategy to address the overpotential issue of non-aqueous lithium-oxygen batteries and also a distinct approach for integrating solar cells and batteries.

Improving the electrocatalytic performance of carbon nanotubes for VO"2"+/VO_2"+ redox reaction by KOH activation

International Nuclear Information System (INIS)

Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

2017-01-01

Highlights: • KOH-activated carbon nanotubes (CNTs) was investigated as superior catalyst for VO"2"+/VO_2"+ redox reaction for vanadium redox flow battery (VRFB) for the first time. • KOH activation for CNTs can result in the chemical etching of surface and improved wettability, accelerating the mass transfer of vanadium ions. • KOH activation can introduce many oxygen-containing groups as active sites on the surface of CNTs. • KOH-activated CNTs as positive catalyst could increase the comprehensive energy storage performance of VRFB. - Abstract: In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO"2"+/VO_2"+ redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO"2"+/VO_2"+ redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO"2"+/VO_2"+ redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO"2"+/VO_2"+ redox reaction for VRFB system.

All-Fullerene-Based Cells for Nonaqueous Redox Flow Batteries.

Science.gov (United States)

Friedl, Jochen; Lebedeva, Maria A; Porfyrakis, Kyriakos; Stimming, Ulrich; Chamberlain, Thomas W

2018-01-10

Redox flow batteries have the potential to revolutionize our use of intermittent sustainable energy sources such as solar and wind power by storing the energy in liquid electrolytes. Our concept study utilizes a novel electrolyte system, exploiting derivatized fullerenes as both anolyte and catholyte species in a series of battery cells, including a symmetric, single species system which alleviates the common problem of membrane crossover. The prototype multielectron system, utilizing molecular based charge carriers, made from inexpensive, abundant, and sustainable materials, principally, C and Fe, demonstrates remarkable current and energy densities and promising long-term cycling stability.

Optimal scheduling for distribution network with redox flow battery storage

International Nuclear Information System (INIS)

Hosseina, Majid; Bathaee, Seyed Mohammad Taghi

2016-01-01

Highlights: • A novel method for optimal scheduling of storages in radial network is presented. • Peak shaving and load leveling are the main objectives. • Vanadium redox flow battery is considered as the energy storage unit. • Real data is used for simulation. - Abstract: There are many advantages to utilize storages in electric power system. Peak shaving, load leveling, load frequency control, integration of renewable, energy trading and spinning reserve are the most important of them. Batteries, especially redox flow batteries, are one of the appropriate storages for utilization in distribution network. This paper presents a novel, heuristic and practical method for optimal scheduling in distribution network with flow battery storage. This heuristic method is more suitable for scheduling and operation of distribution networks which require installation of storages. Peak shaving and load leveling is considered as the main objective in this paper. Several indices are presented in this paper for determine the place of storages and also scheduling for optimal use of energy in them. Simulations of this paper are based on real information of distribution network substation that located in Semnan, Iran.

Zinc and the modulation of redox homeostasis

Science.gov (United States)

Oteiza, Patricia I.

2012-01-01

Zinc, a redox inactive metal, has been long viewed as a component of the antioxidant network, and growing evidence points to its involvement in redox-regulated signaling. These actions are exerted through several mechanisms based on the unique chemical and functional properties of zinc. Overall, zinc contributes to maintain the cell redox balance through different mechanisms including: i) the regulation of oxidant production and metal-induced oxidative damage; ii) the dynamic association of zinc with sulfur in protein cysteine clusters, from which the metal can be released by nitric oxide, peroxides, oxidized glutathione and other thiol oxidant species; iii) zinc-mediated induction of the zinc-binding protein metallothionein, which releases the metal under oxidative conditions and act per se scavenging oxidants; iv) the involvement of zinc in the regulation of glutathione metabolism and of the overall protein thiol redox status; and v) a direct or indirect regulation of redox signaling. Findings of oxidative stress, altered redox signaling, and associated cell/tissue disfunction in cell and animal models of zinc deficiency, stress the relevant role of zinc in the preservation of cell redox homeostasis. However, while the participation of zinc in antioxidant protection, redox sensing, and redox-regulated signaling is accepted, the involved molecules, targets and mechanisms are still partially known and the subject of active research. PMID:22960578

Redox Regulation of Endothelial Cell Fate

Science.gov (United States)

Song, Ping; Zou, Ming-Hui

2014-01-01

Endothelial cells (ECs) are present throughout blood vessels and have variable roles in both physiological and pathological settings. EC fate is altered and regulated by several key factors in physiological or pathological conditions. Reactive nitrogen species and reactive oxygen species derived from NAD(P)H oxidases, mitochondria, or nitric oxide-producing enzymes are not only cytotoxic but also compose a signaling network in the redox system. The formation, actions, key molecular interactions, and physiological and pathological relevance of redox signals in ECs remain unclear. We review the identities, sources, and biological actions of oxidants and reductants produced during EC function or dysfunction. Further, we discuss how ECs shape key redox sensors and examine the biological functions, transcriptional responses, and post-translational modifications evoked by the redox system in ECs. We summarize recent findings regarding the mechanisms by which redox signals regulate the fate of ECs and address the outcome of altered EC fate in health and disease. Future studies will examine if the redox biology of ECs can be targeted in pathophysiological conditions. PMID:24633153

Environmental control of plant nuclear gene expression by chloroplast redox signals

Directory of Open Access Journals (Sweden)

Jeannette ePfalz

2012-11-01

Full Text Available Plant photosynthesis takes place in specialised cell organelles, the chloroplasts, which perform all essential steps of this process. The proteins involved in photosynthesis are encoded by genes located on the plastid and nuclear genomes. Proper function and regulation of light harvesting and energy fixation thus requires a tight coordination of the gene expression machineries in the two genetic compartments. This is achieved by a bi-directional exchange of information between nucleus and plastids. Signals emerging from plastids report the functional and developmental state of the organelle to the nucleus and initiate distinct nuclear gene expression profiles, which trigger responses that support or improve plastid functions. Recent research indicated that this signalling is absolutely essential for plant growth and development. Reduction/oxidation (redox signals from photosynthesis are key players in this information network since they do report functional disturbances in photosynthesis, the primary energy source of plants. Such disturbances are caused by environmental fluctuations for instance in illumination, temperature or water availability. These environmental changes affect the linear electron flow of photosynthesis and result in changes of the redox state of the components involved (e.g. the plastoquinone pool or coupled to it (e.g. the thioredoxin pool. Thus, the changes in redox state directly reflect the environmental impact and serve as immediate plastidial signals to the nucleus. The triggered responses range from counterbalancing reactions within the physiological range up to severe stress responses including cell death. This review focuses on physiological redox signals from photosynthetic electron transport, their relation to the environment, potential transduction pathways to the nucleus and their impact on nuclear gene expression.

Bulk Material Based Thermoelectric Energy Harvesting for Wireless Sensor Applications

International Nuclear Information System (INIS)

Wang, W S; Magnin, W; Wang, N; Hayes, M; O'Flynn, B; O'Mathuna, C

2011-01-01

The trend towards smart building and modern manufacturing demands ubiquitous sensing in the foreseeable future. Self-powered Wireless sensor networks (WSNs) are essential for such applications. This paper describes bulk material based thermoelectric generator (TEG) design and implementation for WSN. A 20cm 2 Bi 0.5 Sb 1.5 Te 3 based TEG was created with optimized configuration and generates 2.7mW in typical condition. A novel load matching method is used to maximize the power output. The implemented power management module delivers 651μW to WSN in 50 deg. C. With average power consumption of Tyndall WSN measured at 72μW, feasibility of utilizing bulk material TEG to power WSN is demonstrated.

Redox Biology in Neurological Function, Dysfunction, and Aging.

Science.gov (United States)

Franco, Rodrigo; Vargas, Marcelo R

2018-04-23

Reduction oxidation (redox) reactions are central to life and when altered, they can promote disease progression. In the brain, redox homeostasis is recognized to be involved in all aspects of central nervous system (CNS) development, function, aging, and disease. Recent studies have uncovered the diverse nature by which redox reactions and homeostasis contribute to brain physiology, and when dysregulated to pathological consequences. Redox reactions go beyond what is commonly described as oxidative stress and involve redox mechanisms linked to signaling and metabolism. In contrast to the nonspecific nature of oxidative damage, redox signaling involves specific oxidation/reduction reactions that regulate a myriad of neurological processes such as neurotransmission, homeostasis, and degeneration. This Forum is focused on the role of redox metabolism and signaling in the brain. Six review articles from leading scientists in the field that appraise the role of redox metabolism and signaling in different aspects of brain biology including neurodevelopment, neurotransmission, aging, neuroinflammation, neurodegeneration, and neurotoxicity are included. An original research article exemplifying these concepts uncovers a novel link between oxidative modifications, redox signaling, and neurodegeneration. This Forum highlights the recent advances in the field and we hope it encourages future research aimed to understand the mechanisms by which redox metabolism and signaling regulate CNS physiology and pathophysiology. Antioxid. Redox Signal. 00, 000-000.

Exercise redox biochemistry: Conceptual, methodological and technical recommendations

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James N. Cobley

2017-08-01

Full Text Available Exercise redox biochemistry is of considerable interest owing to its translational value in health and disease. However, unaddressed conceptual, methodological and technical issues complicate attempts to unravel how exercise alters redox homeostasis in health and disease. Conceptual issues relate to misunderstandings that arise when the chemical heterogeneity of redox biology is disregarded: which often complicates attempts to use redox-active compounds and assess redox signalling. Further, that oxidised macromolecule adduct levels reflect formation and repair is seldom considered. Methodological and technical issues relate to the use of out-dated assays and/or inappropriate sample preparation techniques that confound biochemical redox analysis. After considering each of the aforementioned issues, we outline how each issue can be resolved and provide a unifying set of recommendations. We specifically recommend that investigators: consider chemical heterogeneity, use redox-active compounds judiciously, abandon flawed assays, carefully prepare samples and assay buffers, consider repair/metabolism, use multiple biomarkers to assess oxidative damage and redox signalling. Keywords: Exercise, Oxidative stress, Free radical, Antioxidants, Redox signalling

Communication: energy benchmarking with quantum Monte Carlo for water nano-droplets and bulk liquid water.

Science.gov (United States)

Alfè, D; Bartók, A P; Csányi, G; Gillan, M J

2013-06-14

We show the feasibility of using quantum Monte Carlo (QMC) to compute benchmark energies for configuration samples of thermal-equilibrium water clusters and the bulk liquid containing up to 64 molecules. Evidence that the accuracy of these benchmarks approaches that of basis-set converged coupled-cluster calculations is noted. We illustrate the usefulness of the benchmarks by using them to analyze the errors of the popular BLYP approximation of density functional theory (DFT). The results indicate the possibility of using QMC as a routine tool for analyzing DFT errors for non-covalent bonding in many types of condensed-phase molecular system.

Hydrogen production via thermochemical water-splitting by lithium redox reaction

International Nuclear Information System (INIS)

Nakamura, Naoya; Miyaoka, Hiroki; Ichikawa, Takayuki; Kojima, Yoshitsugu

2013-01-01

Highlights: •Hydrogen production via water-splitting by lithium redox reactions possibly proceeds below 800 °C. •Entropy control by using nonequilibrium technique successfully reduces the reaction temperature. •The operating temperature should be further reduced by optimizing the nonequilibrium condition to control the cycle. -- Abstracts: Hydrogen production via thermochemical water-splitting by lithium redox reactions was investigated as energy conversion technique. The reaction system consists of three reactions, which are hydrogen generation by the reaction of lithium and lithium hydroxide, metal separation by thermolysis of lithium oxide, and oxygen generation by hydrolysis of lithium peroxide. The hydrogen generation reaction completed at 500 °C. The metal separation reaction is thermodynamically difficult because it requires about 3400 °C in equilibrium condition. However, it was indicated from experimental results that the reaction temperature was drastically reduced to 800 °C by using nonequilibrium technique. The hydrolysis reaction was exothermic reaction, and completed by heating up to 300 °C. Therefore, it was expected that the water-splitting by lithium redox reactions was possibly operated below 800 °C under nonequilibrium condition

Analytical redox reactions and redox potentials of tungsten and its concomitants

Energy Technology Data Exchange (ETDEWEB)

Wuensch, G.; Mintrop, L.; Tracht, U.

1985-01-01

It is demonstrated that tungsten can be more effectively determined by redox titrimetry than by gravimetry. In addition to its inherent greater simplicity the volumetric approach offers to determine several components of the sample from consecutive redox titrations. To provide the necessary information the conditional redox potentials of W, Mo, Fe, V, Ti, Sn, Cu, Cr in HCl, HCl + HF and HCl + H/sub 3/PO/sub 4/ have been determined. Use of HF and/or H/sub 3/PO/sub 4/ allows sample preparations without any precipitation of tungstic acid. The influence of these auxiliary complexing agents on the potentials and kinetics is discussed. The titrations can be performed reductimetrically or more conveniently oxidimetrically using potentiometric or amperometric indication. The use of strongly reducing agents restricts the tolerance interval to +-0.6%, so that the gravimetric determination of tungsten remains superior for high precision analyses.

Analytical redox reactions and redox potentials of tungsten and its concomitants

International Nuclear Information System (INIS)

Wuensch, G.; Mintrop, L.; Tracht, U.

1985-01-01

It is demonstrated that tungsten can be more effectively determined by redox titrimetry than by gravimetry. In addition to its inherent greater simplicity the volumetric approach offers to determine several components of the sample from consecutive redox titrations. To provide the necessary information the conditional redox potentials of W, Mo, Fe, V, Ti, Sn, Cu, Cr in HCl, HCl + HF and HCl + H 3 PO 4 have been determined. Use of HF and/or H 3 PO 4 allows sample preparations without any precipitation of tungstic acid. The influence of these auxiliary complexing agents on the potentials and kinetics is discussed. The titrations can be performed reductimetrically or more conveniently oxidimetrically using potentiometric or amperometric indication. The use of strongly reducing agents restricts the tolerance interval to +-0.6%, so that the gravimetric determination of tungsten remains superior for high precision analyses. (orig.) [de

Module 13: Bulk Packaging Shipments by Highway

International Nuclear Information System (INIS)

Przybylski, J.L.

1994-07-01

The Hazardous Materials Modular Training Program provides participating United States Department of Energy (DOE) sites with a basic, yet comprehensive, hazardous materials transportation training program for use onsite. This program may be used to assist individual program entities to satisfy the general awareness, safety training, and function specific training requirements addressed in Code of Federal Regulation (CFR), Title 49, Part 172, Subpart H -- ''Training.'' Module 13 -- Bulk Packaging Shipments by Highway is a supplement to the Basic Hazardous Materials Workshop. Module 13 -- Bulk Packaging Shipments by Highway focuses on bulk shipments of hazardous materials by highway mode, which have additional or unique requirements beyond those addressed in the ten module core program. Attendance in this course of instruction should be limited to those individuals with work experience in transporting hazardous materials utilizing bulk packagings and who have completed the Basic Hazardous Materials Workshop or an equivalent. Participants will become familiar with the rules and regulations governing the transportation by highway of hazardous materials in bulk packagings and will demonstrate the application of these requirements through work projects and examination

Engineered Proteins: Redox Properties and Their Applications

Science.gov (United States)

Prabhulkar, Shradha; Tian, Hui; Wang, Xiaotang; Zhu, Jun-Jie

2012-01-01

Abstract Oxidoreductases and metalloproteins, representing more than one third of all known proteins, serve as significant catalysts for numerous biological processes that involve electron transfers such as photosynthesis, respiration, metabolism, and molecular signaling. The functional properties of the oxidoreductases/metalloproteins are determined by the nature of their redox centers. Protein engineering is a powerful approach that is used to incorporate biological and abiological redox cofactors as well as novel enzymes and redox proteins with predictable structures and desirable functions for important biological and chemical applications. The methods of protein engineering, mainly rational design, directed evolution, protein surface modifications, and domain shuffling, have allowed the creation and study of a number of redox proteins. This review presents a selection of engineered redox proteins achieved through these methods, resulting in a manipulation in redox potentials, an increase in electron-transfer efficiency, and an expansion of native proteins by de novo design. Such engineered/modified redox proteins with desired properties have led to a broad spectrum of practical applications, ranging from biosensors, biofuel cells, to pharmaceuticals and hybrid catalysis. Glucose biosensors are one of the most successful products in enzyme electrochemistry, with reconstituted glucose oxidase achieving effective electrical communication with the sensor electrode; direct electron-transfer-type biofuel cells are developed to avoid thermodynamic loss and mediator leakage; and fusion proteins of P450s and redox partners make the biocatalytic generation of drug metabolites possible. In summary, this review includes the properties and applications of the engineered redox proteins as well as their significance and great potential in the exploration of bioelectrochemical sensing devices. Antioxid. Redox Signal. 17, 1796–1822. PMID:22435347

Radii of Redox Components from Absolute Redox Potentials Compared with Covalent and Aqueous Ionic Radii

Czech Academy of Sciences Publication Activity Database

Heyrovská, Raji

2010-01-01

Roč. 22, č. 9 (2010), s. 903-907 ISSN 1040-0397 Institutional support: RVO:68081707 Keywords : Electrochemistry * Absolute redox potentials * Radii of redox components Subject RIV: BO - Biophysics Impact factor: 2.721, year: 2010

In Situ Redox Manipulation Field Injection Test Report - Hanford 100-H Area

International Nuclear Information System (INIS)

Fruchter, J.S.; Amonette, J.E.; Cole, C.R.

1996-11-01

This report presents results of an In Situ Redox Manipulation (ISRM) Field Injection Withdrawal Test performed at the 100-H Area of the US. Department of Energy's (DOE's) Hanford Site in Washington State in Fiscal Year 1996 by researchers at Pacific Northwest National Laboratory (PNNL). The test is part of the overall ISRM project, the purpose of which is to determine the potential for remediating contaminated groundwater with a technology based on in situ manipulation of subsurface reduction-oxidation (redox) conditions. The ISRM technology would be used to treat subsurface contaminants in groundwater zones at DOE sites

Redox reaction characteristics of riboflavin: a fluorescence spectroelectrochemical analysis and density functional theory calculation.

Science.gov (United States)

Chen, Wei; Chen, Jie-Jie; Lu, Rui; Qian, Chen; Li, Wen-Wei; Yu, Han-Qing

2014-08-01

Riboflavin (RF), the primary redox active component of flavin, is involved in many redox processes in biogeochemical systems. Despite of its wide distribution and important roles in environmental remediation, its redox behaviors and reaction mechanisms in hydrophobic sites remain unclear yet. In this study, spectroelectrochemical analysis and density functional theory (DFT) calculation were integrated to explore the redox behaviors of RF in dimethyl sulfoxide (DMSO), which was used to create a hydrophobic environment. Specifically, cyclic voltafluorometry (CVF) and derivative cyclic voltafluorometry (DCVF) were employed to track the RF concentration changing profiles. It was found that the reduction contained a series of proton-coupled electron transfers dependent of potential driving force. In addition to the electron transfer-chemical reaction-electron transfer process, a disproportionation (DISP1) process was also identified to be involved in the reduction. The redox potential and free energy of each step obtained from the DFT calculations further confirmed the mechanisms proposed based on the experimental results. The combination of experimental and theoretical approaches yields a deep insight into the characteristics of RF in environmental remediation and better understanding about the proton-coupled electron transfer mechanisms. Copyright © 2014 Elsevier B.V. All rights reserved.

Nuclear Matter Bulk Parameter Scales and Correlations

International Nuclear Information System (INIS)

Santos, B. M.; Delfino, A.; Dutra, M.; Lourenço, O.

2015-01-01

We study the arising of correlations among some isovector bulk parameters in nonrelativistic and relativistic hadronic mean-field models. For the former, we investigate correlations in the nonrelativistic (NR) limit of relativistic point-coupling models. We provide analytical correlations, for the NR limit model, between the symmetry energy and its derivatives, namely, the symmetry energy slope, curvature, skewness and fourth order derivative, discussing the conditions in which they are linear ones. We also show that some correlations presented in the NR limit model are reproduced for relativistic models presenting cubic and quartic self-interactions in its scalar field. As a direct application of such linear correlations, we remark its association with possible crossing points in the density dependence of the linearly correlated bulk parameter. (author)

Redox, iron, and nutritional status of children during swimming training.

Science.gov (United States)

Kabasakalis, Athanasios; Kalitsis, Konstantinos; Nikolaidis, Michalis G; Tsalis, George; Kouretas, Dimitris; Loupos, Dimitris; Mougios, Vassilis

2009-11-01

Effects of exercise training on important determinants of children's long-term health, such as redox and iron status, have not been adequately investigated. The aim of the present study was to examine changes in markers of the redox, iron and nutritional status of boy and girl swimmers during a prolonged period of training. 11 boys and 13 girls, aged 10-11 years, were members of a swimming club. They were assessed at the beginning of the training season, at 13 weeks and at 23 weeks through blood sampling and recording of the diet. Reduced glutathione increased at 13 and 23 weeks, whereas oxidised glutathione decreased at 13 weeks, resulting in an increase of the reduced/oxidised glutathione ratio at 13 and 23 weeks. Total antioxidant capacity, catalase, thiobarbituric acid-reactive substances, hemoglobin, transferrin saturation and ferritin did not change significantly. Carbohydrate intake was below 50% of energy and fat intake was above 40% of energy. Intakes of saturated fatty acids and cholesterol were excessive. Iron intake was adequate but intakes of folate, vitamin E, calcium and magnesium did not meet the recommended daily allowances. No significant differences were found between sexes in any of the parameters measured. In conclusion, child swimmers improved the redox status of glutathione during training, although the intake of antioxidant nutrients did not change. The iron status was not impaired by training. Suboptimal intake of several nutrients suggests the need for nutritional monitoring and education of children athletes.

A compartmentalized solute transport model for redox zones in contaminated aquifers: 1. Theory and development

Science.gov (United States)

Abrams , Robert H.; Loague, Keith

2000-01-01

This paper, the first of two parts [see Abrams and Loague, this issue], takes the compartmentalized approach for the geochemical evolution of redox zones presented by Abrams et al. [1998] and embeds it within a solute transport framework. In this paper the compartmentalized approach is generalized to facilitate the description of its incorporation into a solute transport simulator. An equivalent formulation is developed which removes any discontinuities that may occur when switching compartments. Rate‐limited redox reactions are modeled with a modified Monod relationship that allows either the organic substrate or the electron acceptor to be the rate‐limiting reactant. Thermodynamic constraints are used to inhibit lower‐energy redox reactions from occurring under infeasible geochemical conditions without imposing equilibrium on the lower‐energy reactions. The procedure used allows any redox reaction to be simulated as being kinetically limited or thermodynamically limited, depending on local geochemical conditions. Empirical reaction inhibition methods are not needed. The sequential iteration approach (SIA), a technique which allows the number of solute transport equations to be reduced, is adopted to solve the coupled geochemical/solute transport problem. When the compartmentalized approach is embedded within the SIA, with the total analytical concentration of each component as the dependent variable in the transport equation, it is possible to reduce the number of transport equations even further than with the unmodified SIA. A one‐dimensional, coupled geochemical/solute transport simulation is presented in which redox zones evolve dynamically in time and space. The compartmentalized solute transport (COMPTRAN) model described in this paper enables the development of redox zones to be simulated under both kinetic and thermodynamic constraints. The modular design of COMPTRAN facilitates the use of many different, preexisting solute transport and

Renormalization group approach to causal bulk viscous cosmological models

International Nuclear Information System (INIS)

Belinchon, J A; Harko, T; Mak, M K

2002-01-01

The renormalization group method is applied to the study of homogeneous and flat Friedmann-Robertson-Walker type universes, filled with a causal bulk viscous cosmological fluid. The starting point of the study is the consideration of the scaling properties of the gravitational field equations, the causal evolution equation of the bulk viscous pressure and the equations of state. The requirement of scale invariance imposes strong constraints on the temporal evolution of the bulk viscosity coefficient, temperature and relaxation time, thus leading to the possibility of obtaining the bulk viscosity coefficient-energy density dependence. For a cosmological model with bulk viscosity coefficient proportional to the Hubble parameter, we perform the analysis of the renormalization group flow around the scale-invariant fixed point, thereby obtaining the long-time behaviour of the scale factor

Characterization of the surface redox process of adsorbed morin at glassy carbon electrodes

International Nuclear Information System (INIS)

Tesio, Alvaro Yamil; Granero, Adrian Marcelo; Fernandez, Hector; Zon, Maria Alicia

2011-01-01

The thermodynamic and kinetics of the adsorption of morin (MOR) on glassy carbon (GC) electrodes in 0.2 mol dm -3 phosphate buffer solutions (PBS, pH 7.00) was studied by both cyclic (CV) and square wave (SWV) voltammetries. The Frumkin adsorption isotherm was the best to describe the specific interaction of MOR with GC electrodes. The SWV allowed to characterize the thermodynamic and kinetics of surface quasi-reversible redox couple of MOR, using the combination of the 'quasi-reversible maximum' and the 'splitting of SW net peaks' methods. Average values obtained for the formal potential and the anodic transfer coefficient were (0.27 ± 0.02) V and (0.59 ± 0.09), respectively. Moreover, a value of formal rate constant (k s ) of 87 s -1 for the overall two-electron redox process was calculated. The SWV was also employed to generate calibration curves, which were linear in the range MOR bulk concentration (c MOR *) from 1.27 x 10 -7 to 2.50 x 10 -5 mol dm -3 . The lowest concentration experimentally measured for a signal to noise ratio of 3:1 was 1.25 x 10 -8 mol dm -3 (3 ppb).

Simultaneous anionic and cationic redox

Science.gov (United States)

Jung, Sung-Kyun; Kang, Kisuk

2017-12-01

It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

A novel and high-effective redox-mediated gel polymer electrolyte for supercapacitor

International Nuclear Information System (INIS)

Ma, Guofu; Feng, Enke; Sun, Kanjun; Peng, Hui; Li, Jiajia; Lei, Ziqiang

2014-01-01

Graphical abstract: - Highlights: • Alkali and P-phenylenediamine doped polyvinyl alcohol gel electrolyte is prepared. • The PVA-KOH-PPD gel electrolyte can also be used as separator. • The introduction of PPD increases the ionic conductivity of electrolyte. • The supercapacitor exhibits flexible and high energy density. - Abstract: A supercapacitor utilize a novel redox-mediated gel polymer (PVA-KOH-PPD) as electrolyte and separator, and activated carbon as electrodes is assembled. The PVA-KOH-PPD gel polymer as potential electrolyte for supercapacitor is investigated by cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy techniques. It is found that the supercapacitor exhibits high ionic conductivity (25 mS cm −1 ), large electrode specific capacitance (611 F g −1 ) and high energy density (82.56 Wh kg −1 ). The high performance is attributed to the addition of quick redox reactions at the electrolyte|electrode interface as PPD undergoes a two-proton/two-electron reduction and oxidation during cycling. Furthermore, the supercapacitor with PVA-KOH-PPD gel polymer shows excellent charge-discharge stability, after 1000 charge-discharge cycles, the supercapacitor still retains a high electrode specific capacitance of 470 F g −1 . It is believed that the idea using redox mediator has a good prospect for improving the performances of supercapacitors

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

Science.gov (United States)

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

2015-07-20

Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all-organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical-based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A comparative study on the solubility and stability of p-phenylenediamine-based organic redox couples for non-aqueous flow batteries

Science.gov (United States)

Kim, Hyun-seung; Lee, Keon-Joon; Han, Young-Kyu; Ryu, Ji Heon; Oh, Seung M.

2017-04-01

A methyl-substituted p-phenylenediamine (PD), N,N,N‧,N‧-tetramethyl-p-phenylenediamine (TMPD), is examined as a positive redox couple with high energy density for non-aqueous Li-flow batteries. Methyl substitution affects the solubility of the redox couple, as the solubility is increased by a factor of ten, to a maximum solubility of 5.0 M in 1.0 M lithium tetrafluoroborate-propylene carbonate supporting electrolyte due to elimination of the hydrogen bonding between the solute molecules. The methyl substitution also enhances the chemical stability of the cation radical and di-cation being generated from PD, as the redox center is shielded by the methyl groups. Furthermore, this organic redox couple demonstrate two-electron redox reactions at 3.2 and 3.8 V (vs. Li/Li+); therefore, the volumetric capacity is twice higher compared to conventional one-electron involved redox couples. In a non-flowing Li/TMPD coin-cell, this organic redox couple demonstrates very stable cycleability as a positive redox couple for non-aqueous flow batteries.

Redox-assisted Li+-storage in lithium-ion batteries

International Nuclear Information System (INIS)

Huang Qizhao; Wang Qing

2016-01-01

Interfacial charge transfer is the key kinetic process dictating the operation of lithium-ion battery. Redox-mediated charge propagations of the electronic (e − and h + ) and ionic species (Li + ) at the electrode–electrolyte interface have recently gained increasing attention for better exploitation of battery materials. This article briefly summarises the energetic and kinetic aspects of lithium-ion batteries, and reviews the recent progress on various redox-assisted Li + storage approaches. From molecular wiring to polymer wiring and from redox targeting to redox flow lithium battery, the role of redox mediators and the way of the redox species functioning in lithium-ion batteries are discussed. (topical review)

Exercise-intensity dependent alterations in plasma redox status do not reflect skeletal muscle redox-sensitive protein signaling.

Science.gov (United States)

Parker, Lewan; Trewin, Adam; Levinger, Itamar; Shaw, Christopher S; Stepto, Nigel K

2018-04-01

Redox homeostasis and redox-sensitive protein signaling play a role in exercise-induced adaptation. The effects of sprint-interval exercise (SIE), high-intensity interval exercise (HIIE) and continuous moderate-intensity exercise (CMIE), on post-exercise plasma redox status are unclear. Furthermore, whether post-exercise plasma redox status reflects skeletal muscle redox-sensitive protein signaling is unknown. In a randomized crossover design, eight healthy adults performed a cycling session of HIIE (5×4min at 75% W max ), SIE (4×30s Wingate's), and CMIE work-matched to HIIE (30min at 50% of W max ). Plasma hydrogen peroxide (H 2 O 2 ), thiobarbituric acid reactive substances (TBARS), superoxide dismutase (SOD) activity, and catalase activity were measured immediately post, 1h, 2h and 3h post-exercise. Plasma redox status biomarkers were correlated with phosphorylation of skeletal muscle p38-MAPK, JNK, NF-κB, and IκBα protein content immediately and 3h post-exercise. Plasma catalase activity was greater with SIE (56.6±3.8Uml -1 ) compared to CMIE (42.7±3.2, pexercise plasma TBARS and SOD activity significantly (pexercise protocol. A significant positive correlation was detected between plasma catalase activity and skeletal muscle p38-MAPK phosphorylation 3h post-exercise (r=0.40, p=0.04). No other correlations were detected (all p>0.05). Low-volume SIE elicited greater post-exercise plasma catalase activity compared to HIIE and CMIE, and greater H 2 O 2 compared to CMIE. Plasma redox status did not, however, adequately reflect skeletal muscle redox-sensitive protein signaling. Copyright © 2017 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Thiol/disulfide redox states in signaling and sensing

Science.gov (United States)

Go, Young-Mi; Jones, Dean P.

2015-01-01

Rapid advances in redox systems biology are creating new opportunities to understand complexities of human disease and contributions of environmental exposures. New understanding of thiol-disulfide systems have occurred during the past decade as a consequence of the discoveries that thiol and disulfide systems are maintained in kinetically controlled steady-states displaced from thermodynamic equilibrium, that a widely distributed family of NADPH oxidases produces oxidants that function in cell signaling, and that a family of peroxiredoxins utilize thioredoxin as a reductant to complement the well-studied glutathione antioxidant system for peroxide elimination and redox regulation. This review focuses on thiol/disulfide redox state in biologic systems and the knowledge base available to support development of integrated redox systems biology models to better understand the function and dysfunction of thiol-disulfide redox systems. In particular, central principles have emerged concerning redox compartmentalization and utility of thiol/disulfide redox measures as indicators of physiologic function. Advances in redox proteomics show that, in addition to functioning in protein active sites and cell signaling, cysteine residues also serve as redox sensors to integrate biologic functions. These advances provide a framework for translation of redox systems biology concepts to practical use in understanding and treating human disease. Biological responses to cadmium, a widespread environmental agent, are used to illustrate the utility of these advances to the understanding of complex pleiotropic toxicities. PMID:23356510

Bulk renormalization and particle spectrum in codimension-two brane worlds

International Nuclear Information System (INIS)

Salvio, Alberto

2013-01-01

We study the Casimir energy due to bulk loops of matter fields in codimension-two brane worlds and discuss how effective field theory methods allow us to use this result to renormalize the bulk and brane operators. In the calculation we explicitly sum over the Kaluza-Klein (KK) states with a new convenient method, which is based on a combined use of zeta function and dimensional regularization. Among the general class of models we consider we include a supersymmetric example, 6D gauged chiral supergravity. Although much of our discussion is more general, we treat in some detail a class of compactifications, where the extra dimensions parametrize a rugby ball shaped space with size stabilized by a bulk magnetic flux. The rugby ball geometry requires two branes, which can host the Standard Model fields and carry both tension and magnetic flux (of the bulk gauge field), the leading terms in a derivative expansion. The brane properties have an impact on the KK spectrum and therefore on the Casimir energy as well as on the renormalization of the brane operators. A very interesting feature is that when the two branes carry exactly the same amount of flux, one half of the bulk supersymmetries survives after the compactification, even if the brane tensions are large. We also discuss the implications of these calculations for the natural value of the cosmological constant when the bulk has two large extra dimensions and the bulk supersymmetry is partially preserved (or completely broken).

Development of greenhouse solar systems for bulk tobacco curing and plant production

Energy Technology Data Exchange (ETDEWEB)

Huang, B.K.; Bowers, C.G. Jr.

1986-12-01

Among many farm crops, bright leaf tobacco is the most energy- and labor-intensive crop. The greenhouse solar system (solar bulk-curing/greenhouse system, or solar barn) was developed to provide multiple-use facilities for year-round solar energy utilization to save fossil fuels in tobacco curing and plant production and to facilitate the total mechanization of tobacco culture. Two types of full-size greenhouse solar systems, the load-supporting wall design and the shell design, both utilizing the thermal envelope concept, were designed and constructed for solar bulk-curing of tobacco, growing transplants and horticultural crops under controlled environment, and aiding automation of transplanting operations. Full-scale field tests of solar bulk curing showed that the fuel savings were consistantly improved from 37% in 1975 to 51% in 1978 for this solar bulk-curing system as compared with a conventional bulk-curing barn as a control. The feasibility of the system to save energy by using solar energy as a first priority source was significantly demonstrated. Three-year greenhouse and field tests showed that high germination rate of 95-97% with excellent emergence frequency was obtained for tobacco seeds under the controlled environment provided by the greenhouse solar system. In general, the containerized transplants from greenhouse solar system significantly exceeded the conventional bare-root transplants in growth, leaf-quality and yield. 9 figs., 3 tabs., 10 refs.

Redox homeostasis: The Golden Mean of healthy living

Directory of Open Access Journals (Sweden)

Fulvio Ursini

2016-08-01

Full Text Available The notion that electrophiles serve as messengers in cell signaling is now widely accepted. Nonetheless, major issues restrain acceptance of redox homeostasis and redox signaling as components of maintenance of a normal physiological steady state. The first is that redox signaling requires sudden switching on of oxidant production and bypassing of antioxidant mechanisms rather than a continuous process that, like other signaling mechanisms, can be smoothly turned up or down. The second is the misperception that reactions in redox signaling involve “reactive oxygen species” rather than reaction of specific electrophiles with specific protein thiolates. The third is that hormesis provides protection against oxidants by increasing cellular defense or repair mechanisms rather than by specifically addressing the offset of redox homeostasis. Instead, we propose that both oxidant and antioxidant signaling are main features of redox homeostasis. As the redox shift is rapidly reversed by feedback reactions, homeostasis is maintained by continuous signaling for production and elimination of electrophiles and nucleophiles. Redox homeostasis, which is the maintenance of nucleophilic tone, accounts for a healthy physiological steady state. Electrophiles and nucleophiles are not intrinsically harmful or protective, and redox homeostasis is an essential feature of both the response to challenges and subsequent feedback. While the balance between oxidants and nucleophiles is preserved in redox homeostasis, oxidative stress provokes the establishment of a new radically altered redox steady state. The popular belief that scavenging free radicals by antioxidants has a beneficial effect is wishful thinking. We propose, instead, that continuous feedback preserves nucleophilic tone and that this is supported by redox active nutritional phytochemicals. These nonessential compounds, by activating Nrf2, mimic the effect of endogenously produced electrophiles

Exercise redox biochemistry: Conceptual, methodological and technical recommendations.

Science.gov (United States)

Cobley, James N; Close, Graeme L; Bailey, Damian M; Davison, Gareth W

2017-08-01

Exercise redox biochemistry is of considerable interest owing to its translational value in health and disease. However, unaddressed conceptual, methodological and technical issues complicate attempts to unravel how exercise alters redox homeostasis in health and disease. Conceptual issues relate to misunderstandings that arise when the chemical heterogeneity of redox biology is disregarded: which often complicates attempts to use redox-active compounds and assess redox signalling. Further, that oxidised macromolecule adduct levels reflect formation and repair is seldom considered. Methodological and technical issues relate to the use of out-dated assays and/or inappropriate sample preparation techniques that confound biochemical redox analysis. After considering each of the aforementioned issues, we outline how each issue can be resolved and provide a unifying set of recommendations. We specifically recommend that investigators: consider chemical heterogeneity, use redox-active compounds judiciously, abandon flawed assays, carefully prepare samples and assay buffers, consider repair/metabolism, use multiple biomarkers to assess oxidative damage and redox signalling. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

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. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of a Vanadium Redox Flow Battery with Hydrogen generation

OpenAIRE

Wrang, Daniel

2016-01-01

We consider the modelling and optimal control of energy storage systems, in this study a Vanadium Redox Flow Battery. Such a battery can be introduced in the electrical grid to be charged when demand is low and discharged when demand is high, increasing the overall efficiency of the network while reducing costs and emission of greenhouse gases. The model of the battery proposed in this study is less complex than the majority of models on batteries and energy storage systems found in literatur...

Big bang nucleosynthesis constraints on bulk neutrinos

International Nuclear Information System (INIS)

Goh, H.S.; Mohapatra, R.N.

2002-01-01

We examine the constraints imposed by the requirement of successful nucleosynthesis on models with one large extra hidden space dimension and a single bulk neutrino residing in this dimension. We solve the Boltzmann kinetic equation for the thermal distribution of the Kaluza-Klein modes and evaluate their contribution to the energy density at the big bang nucleosynthesis epoch to constrain the size of the extra dimension R -1 ≡μ and the parameter sin 2 2θ which characterizes the mixing between the active and bulk neutrinos

Quantifying TEMPO Redox Polymer Charge Transport toward the Organic Radical Battery.

Science.gov (United States)

Karlsson, Christoffer; Suga, Takeo; Nishide, Hiroyuki

2017-03-29

To design new and better organic active battery materials in a rational fashion, fundamental parameters of the charge transport must be studied. Herein we report on the electronic conductivity by electron diffusion in a TEMPO-containing redox polymer, and the reorganization energy of the TEMPO self-exchange in an organic solvent is determined for the first time. The electronic conductivity was 8.5 μS/cm at E 0 and corresponded to a redox hopping mechanism. The apparent electron diffusion coefficient was 1.9 × 10 -9 cm 2 /s at room temperature, and at short times the ion diffusion was limiting with a diffusion coefficient of 6.5 × 10 -10 cm 2 /s. The reorganization energy was determined to be 1.01 eV, indicating a rather polar chemical environment for the TEMPO groups. The implications for the usage of this type of materials in organic energy storage are discussed. As conductivity through 10 μm was demonstrated, we show that, if sufficient swellability can be ensured, charge can be transported through several micrometer thick layers in a battery electrode without any conducting additive.

Redox control of molecular motion in switchable artificial nanoscale devices.

Science.gov (United States)

Credi, Alberto; Semeraro, Monica; Silvi, Serena; Venturi, Margherita

2011-03-15

The design, synthesis, and operation of molecular-scale systems that exhibit controllable motions of their component parts is a topic of great interest in nanoscience and a fascinating challenge of nanotechnology. The development of this kind of species constitutes the premise to the construction of molecular machines and motors, which in a not-too-distant future could find applications in fields such as materials science, information technology, energy conversion, diagnostics, and medicine. In the past 25 years the development of supramolecular chemistry has enabled the construction of an interesting variety of artificial molecular machines. These devices operate via electronic and molecular rearrangements and, like the macroscopic counterparts, they need energy to work as well as signals to communicate with the operator. Here we outline the design principles at the basis of redox switching of molecular motion in artificial nanodevices. Redox processes, chemically, electrically, or photochemically induced, can indeed supply the energy to bring about molecular motions. Moreover, in the case of electrically and photochemically induced processes, electrochemical and photochemical techniques can be used to read the state of the system, and thus to control and monitor the operation of the device. Some selected examples are also reported to describe the most representative achievements in this research area.

High performance, flexible, poly(3,4-ethylenedioxythiophene) supercapacitors achieved by doping redox mediators in organogel electrolytes

Science.gov (United States)

Zhang, Huanhuan; Li, Jinyu; Gu, Cheng; Yao, Mingming; Yang, Bing; Lu, Ping; Ma, Yuguang

2016-11-01

The relatively low energy density is now a central issue hindering the development of supercapacitors as energy storage devices. Various approaches are thus developed to enhance the energy density, mainly centering on the fabrication of electrode materials or optimization of cell configurations. Compared with these approaches, modifications in electrolytes are much simple and versatile. Herein, we integrate the wide voltages endowed by organic electrolytes and the additional capacitances brought by redox mediators, to fabricate high energy density supercapacitors. On the basis of this idea, supercapacitors with poly(3,4-ethylenedioxythiophene) (PEDOT) as electrode material exhibit extended operating voltage of 1.5 V, extraordinary capacitance of 363 F g-1 and high energy density of 27.4 Wh kg-1. The redox mediators reported here, ferrocene and 4-oxo-2,2,6,6-tetramethylpiperidinooxy, are the first time being applied in supercapacitors, especially in the gel state. While providing additional faradaic capacitances, they also exhibit synergistic interaction with PEDOT and improve the cycling stability of supercapacitors.

Polyoxovanadate-alkoxide clusters as multi-electron charge carriers for symmetric non-aqueous redox flow batteries.

Science.gov (United States)

VanGelder, L E; Kosswattaarachchi, A M; Forrestel, P L; Cook, T R; Matson, E M

2018-02-14

Non-aqueous redox flow batteries have emerged as promising systems for large-capacity, reversible energy storage, capable of meeting the variable demands of the electrical grid. Here, we investigate the potential for a series of Lindqvist polyoxovanadate-alkoxide (POV-alkoxide) clusters, [V 6 O 7 (OR) 12 ] (R = CH 3 , C 2 H 5 ), to serve as the electroactive species for a symmetric, non-aqueous redox flow battery. We demonstrate that the physical and electrochemical properties of these POV-alkoxides make them suitable for applications in redox flow batteries, as well as the ability for ligand modification at the bridging alkoxide moieties to yield significant improvements in cluster stability during charge-discharge cycling. Indeed, the metal-oxide core remains intact upon deep charge-discharge cycling, enabling extremely high coulombic efficiencies (∼97%) with minimal overpotential losses (∼0.3 V). Furthermore, the bulky POV-alkoxide demonstrates significant resistance to deleterious crossover, which will lead to improved lifetime and efficiency in a redox flow battery.

Bulk viscosity of hot dense Quark matter in the PNJL model

International Nuclear Information System (INIS)

Xiao Shisong; Guo Panpan; Zhang Le; Hou Defu

2014-01-01

Starting from the Kubo formula and the QCD low energy theorem, we study the the bulk viscosity of hot dense quark matter in the PNJL model from the equation of state. We show that the bulk viscosity has a sharp peak near the chiral phase transition, and that the ratio of bulk viscosity over entropy rises dramatically in the vicinity of the phase transition. These results agree with those from the lattice and other model calculations. In addition, we show that the increase of chemical potential raises the bulk viscosity. (authors)

Redox potentials and kinetics of the Ce 3+/Ce 4+ redox reaction and solubility of cerium sulfates in sulfuric acid solutions

Science.gov (United States)

Paulenova, A.; Creager, S. E.; Navratil, J. D.; Wei, Y.

Experimental work was performed with the aim of evaluating the Ce 4+/Ce 3+ redox couple in sulfuric acid electrolyte for use in redox flow battery (RFB) technology. The solubility of cerium sulfates in 0.1-4.0 M sulfuric acid at 20-60 °C was studied. A synergistic effect of both sulfuric acid concentration and temperature on the solubility of cerous sulfate was observed. The solubility of cerous sulfate significantly decreased with rising concentration of sulfuric acid and rising temperature, while the solubility of ceric sulfate goes through a significant maximum at 40 °C. Redox potentials and the kinetics of the cerous/ceric redox reaction were also studied under the same temperature-concentration conditions. The redox potentials were measured using the combined redox electrode (Pt-Ag/AgCl) in equimolar Ce 4+/Ce 3+ solutions (i.e.[Ce 3+]=[Ce 4+]) in sulfuric acid electrolyte. The Ce 3+/Ce 4+ redox potentials significantly decrease (i.e. shift to more negative values) with rising sulfuric acid concentration; a small maximum is observed at 40 °C. Cyclic voltammetric experiments confirmed slow electrochemical kinetics of the Ce 3+/Ce 4+ redox reaction on carbon glassy electrodes (CGEs) in sulfuric acid solutions. The observed dependencies of solubilities, the redox potentials and the kinetics of Ce 3+/Ce 4+ redox reaction on sulfuric acid concentration are thought to be the result of inequivalent complexation of the two redox species by sulfate anions: the ceric ion is much more strongly bound to sulfate than is the cerous ion. The best temperature-concentration conditions for the RFB electrolytes appear to be 40 °C and 1 M sulfuric acid, where the relatively good solubility of both cerium species, the maximum of redox potentials, and the more or less satisfying stability of CGE s were found. Even so, the relatively low solubility of cerium salts in sulfuric acid media and slow redox kinetics of the Ce 3+/Ce 4+ redox reaction at carbon indicate that the Ce 3+/Ce

Multiple redox states of multiheme cytochromes may enable bacterial response to changing redox environments

Science.gov (United States)

Arbour, T.; Wrighton, K. C.; Mullin, S. W.; Castelle, C.; Luef, B.; Gilbert, B.; Banfield, J. F.

2013-12-01

Multiheme c-type cytochromes (MHCs) are key components in electron-transport pathways that enable some microorganisms to transfer electron byproducts of metabolism to a variety of minerals. As a response to changes in mineral redox potential, microbial communities may shift their membership, or individual organisms may adjust protein expression. Alternatively, the ability to respond may be conferred by the innate characteristics of certain electron-transport-chain components. Here, we used potentiostat-controlled microbial fuel cells (MFCs) to measure the timescale of response to imposed changes in redox conditions, thus placing constraints on the importance of these different mechanisms. In the experiments, a solid electrode acts as an electron-accepting mineral whose redox potential can be precisely controlled. We inoculated duplicate MFCs with a sediment/groundwater mixture from an aquifer at Rifle, Colorado, supplied acetate as an electron donor, and obtained stable, mixed-species biofilms dominated by Geobacter and a novel Geobacter-related family. We poised the anode at potentials spanning the range of natural Fe(III)-reduction, then performed cyclic voltammetry (CV) to characterize the overall biofilm redox signature. The apparent biofilm midpoint potential shifted directly with anode set potential when the latter was changed within the range from about -250 to -50 mV vs. SHE. Following a jump in set potential by 200 mV, the CV-midpoint shift by ~100 mV over a timescale of ~30 minutes to a few hours, depending on the direction of the potential change. The extracellular electron transfer molecules, whose overall CV signature is very similar to those of purified MHCs, appear to span a broad redox range (~200 mV), supporting the hypothesis that MHCs confer substantial redox flexibility. This flexibility may be a principle reason for the abundance of MHCs expressed by microorganisms capable of extracellular electron transfer to minerals.

Pyridine nucleotides in regulation of cell death and survival by redox and non-redox reactions.

Science.gov (United States)

Novak Kujundžić, Renata; Žarković, Neven; Gall Trošelj, Koraljka

2014-01-01

Changes of the level and ratios of pyridine nucleotides determine metabolism- dependent cellular redox status and the activity of poly(ADP-ribose) polymerases (PARPs) and sirtuins, thereby influencing several processes closely related to cell survival and death. Pyridine nucleotides participate in numerous metabolic reactions whereby their net cellular level remains constant, but the ratios of NAD+/NADP+ and NADH/NADPH oscillate according to metabolic changes in response to diverse stress signals. In non-redox reactions, NAD+ is degraded and quickly, afterward, resynthesized in the NAD+ salvage pathway, unless overwhelming activation of PARP-1 consumes NAD+ to the point of no return, when the cell can no longer generate enough ATP to accommodate NAD+ resynthesis. The activity of PARP-1 is mandatory for the onset of cytoprotective autophagy on sublethal stress signals. It has become increasingly clear that redox status, largely influenced by the metabolism-dependent composition of the pyridine nucleotides pool, plays an important role in the synthesis of pro-apoptotic and anti-apoptotic sphingolipids. Awareness of the involvement of the prosurvival sphingolipid, sphingosine-1-phosphate, in transition from inflammation to malignant transformation has recently emerged. Here, the participation of pyridine nucleotides in redox and non-redox reactions, sphingolipid metabolism, and their role in cell fate decisions is reviewed.

Multi-Fluid Geo-Energy Systems for Bulk and Thermal Energy Storage and Dispatchable Renewable and Low-Carbon Electricity

Science.gov (United States)

Buscheck, T. A.; Randolph, J.; Saar, M. O.; Hao, Y.; Sun, Y.; Bielicki, J. M.

2014-12-01

Integrating renewable energy sources into electricity grids requires advances in bulk and thermal energy storage technologies, which are currently expensive and have limited capacity. We present an approach that uses the huge fluid and thermal storage capacity of the subsurface to harvest, store, and dispatch energy from subsurface (geothermal) and surface (solar, nuclear, fossil) thermal resources. CO2 captured from fossil-energy systems and N2 separated from air are injected into permeable formations to store pressure, generate artesian flow of brine, and provide additional working fluids. These enable efficient fluid recirculation, heat extraction, and power conversion, while adding operational flexibility. Our approach can also store and dispatch thermal energy, which can be used to levelize concentrating solar power and mitigate variability of wind and solar power. This may allow low-carbon, base-load power to operate at full capacity, with the stored excess energy being available to addresss diurnal and seasonal mismatches between supply and demand. Concentric rings of horizontal injection and production wells are used to create a hydraulic divide to store pressure, CO2, N2, and thermal energy. Such storage can take excess power from the grid and excess thermal energy, and dispatch that energy when it is demanded. The system is pressurized and/or heated when power supply exceeds demand and depressurized when demand exceeds supply. Supercritical CO2 and N2 function as cushion gases to provide enormous pressure-storage capacity. Injecting CO2 and N2 displaces large quantities of brine, reducing the use of fresh water. Geologic CO2 storage is a crucial option for reducing CO2 emissions, but valuable uses for CO2 are needed to justify capture costs. The initial "charging" of our system requires permanently isolating large volumes of CO2 from the atmosphere and thus creates a market for its disposal. Our approach is designed for locations where a permeable

Glutathione redox potential in the mitochondrial intermembrane space is linked to the cytosol and impacts the Mia40 redox state

Science.gov (United States)

Kojer, Kerstin; Bien, Melanie; Gangel, Heike; Morgan, Bruce; Dick, Tobias P; Riemer, Jan

2012-01-01

Glutathione is an important mediator and regulator of cellular redox processes. Detailed knowledge of local glutathione redox potential (EGSH) dynamics is critical to understand the network of redox processes and their influence on cellular function. Using dynamic oxidant recovery assays together with EGSH-specific fluorescent reporters, we investigate the glutathione pools of the cytosol, mitochondrial matrix and intermembrane space (IMS). We demonstrate that the glutathione pools of IMS and cytosol are dynamically interconnected via porins. In contrast, no appreciable communication was observed between the glutathione pools of the IMS and matrix. By modulating redox pathways in the cytosol and IMS, we find that the cytosolic glutathione reductase system is the major determinant of EGSH in the IMS, thus explaining a steady-state EGSH in the IMS which is similar to the cytosol. Moreover, we show that the local EGSH contributes to the partially reduced redox state of the IMS oxidoreductase Mia40 in vivo. Taken together, we provide a comprehensive mechanistic picture of the IMS redox milieu and define the redox influences on Mia40 in living cells. PMID:22705944

Degree of glutathione deficiency and redox imbalance depend on subtype of mitochondrial disease and clinical status.

Directory of Open Access Journals (Sweden)

Gregory M Enns

Full Text Available Mitochondrial disorders are associated with decreased energy production and redox imbalance. Glutathione plays a central role in redox signaling and protecting cells from oxidative damage. In order to understand the consequences of mitochondrial dysfunction on in vivo redox status, and to determine how this varies by mitochondrial disease subtype and clinical severity, we used a sensitive tandem mass spectrometry assay to precisely quantify whole blood reduced (GSH and oxidized (GSSG glutathione levels in a large cohort of mitochondrial disorder patients. Glutathione redox potential was calculated using the Nernst equation. Compared to healthy controls (n = 59, mitochondrial disease patients (n = 58 as a group showed significant redox imbalance (redox potential -251 mV ± 9.7, p<0.0001 with an increased level of oxidation by ∼ 9 mV compared to controls (-260 mV ± 6.4. Underlying this abnormality were significantly lower whole blood GSH levels (p = 0.0008 and GSH/GSSG ratio (p = 0.0002, and significantly higher GSSG levels (p<0.0001 in mitochondrial disease patients compared to controls. Redox potential was significantly more oxidized in all mitochondrial disease subgroups including Leigh syndrome (n = 15, electron transport chain abnormalities (n = 10, mitochondrial encephalomyopathy, lactic acidosis and stroke-like episodes (n = 8, mtDNA deletion syndrome (n = 7, mtDNA depletion syndrome (n = 7, and miscellaneous other mitochondrial disorders (n = 11. Patients hospitalized in metabolic crisis (n = 7 showed the greatest degree of redox imbalance at -242 mV ± 7. Peripheral whole blood GSH and GSSG levels are promising biomarkers of mitochondrial dysfunction, and may give insights into the contribution of oxidative stress to the pathophysiology of the various mitochondrial disorders. In particular, evaluation of redox potential may be useful in monitoring of clinical status or response to redox-modulating therapies in clinical trials.

Characterization of redox conditions in groundwater contaminant plumes

Science.gov (United States)

Christensen, Thomas H.; Bjerg, Poul L.; Banwart, Steven A.; Jakobsen, Rasmus; Heron, Gorm; Albrechtsen, Hans-Jørgen

2000-10-01

Evaluation of redox conditions in groundwater pollution plumes is often a prerequisite for understanding the behaviour 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 cases have been reported. No standardised or generally accepted approach exists. Slow electrode kinetics and the common lack of internal equilibrium of redox processes in pollution plumes make, with a few exceptions, direct electrochemical measurement and rigorous interpretation of redox potentials dubious, if not erroneous. Several other approaches have been used in addressing redox conditions in pollution plumes: redox-sensitive compounds in groundwater samples, hydrogen concentrations in groundwater, concentrations of volatile fatty acids in groundwater, sediment characteristics and microbial tools, such as MPN counts, PLFA biomarkers and redox bioassays. This paper reviews the principles behind the different approaches, summarizes methods used and evaluates the approaches based on the experience from the reported applications.

Calculation of the redox potential of the protein azurin and some mutants

NARCIS (Netherlands)

van den Bosch, M; Swart, M; Snijders, JG; Berendsen, HJC; Mark, AE; Oostenbrink, C; van Gunsteren, WF; Canters, GW

Azurin from Pseudomonas aeruginosa is a small 128-residue, copper-containing protein. Its redox potential can be modified by mutating the protein. Free-energy calculations based on classical molecular-dynamics simulations of the protein and from mutants in aqueous solution at different pH values

Multi-physics Model for the Aging Prediction of a Vanadium Redox Flow Battery System

International Nuclear Information System (INIS)

Merei, Ghada; Adler, Sophie; Magnor, Dirk; Sauer, Dirk Uwe

2015-01-01

Highlights: • Present a multi-physics model of vanadium redox-flow battery. • This model is essential for aging prediction. • It is applicable for VRB system of different power and capacity ratings. • Good results comparing with current research in this field. - Abstract: The all-vanadium redox-flow battery is an attractive candidate to compensate the fluctuations of non-dispatchable renewable energy generation. While several models for vanadium redox batteries have been described yet, no model has been published, which is adequate for the aging prediction. Therefore, the present paper presents a multi-physics model which determines all parameters that are essential for an aging prediction. In a following paper, the corresponding aging model of vanadium redox flow battery (VRB) is described. The model combines existing models for the mechanical losses and temperature development with new approaches for the batteries side reactions. The model was implemented in Matlab/Simulink. The modeling results presented in the paper prove to be consistent with the experimental results of other research groups

Redox kinetics and mechanism in silicate melts

International Nuclear Information System (INIS)

Cochain, B.

2009-12-01

This work contributes to better understand iron redox reactions and mechanisms in silicate melts. It was conducted on compositions in both Na 2 O-B 2 O 3 -SiO 2 -FeO and Na 2 O-Al 2 O 3 -SiO 2 -FeO systems. The influence of boron-sodium and aluminum-sodium substitutions and iron content on properties and structure of glasses and on the iron redox kinetics has been studied by Raman, Moessbauer and XANES spectroscopies at the B and Fe K-edges. In borosilicate glasses, an increase in iron content or in the Fe 3+ /ΣFe redox state implies a structural rearrangement of the BO 4 species in the glass network whereas the BO 3 and BO 4 relative proportions remain nearly constant. In all studied glasses and melts, Fe 3+ is a network former in tetrahedral coordination, unless for aluminosilicates of ratio Al/Na≥1 where Fe 3+ is a network modifier in five-fold coordination. Near Tg, diffusion of network modifying cations controls the iron redox kinetics along with a flux of electron holes. At liquidus temperatures, oxygen diffusion is considered to be the mechanism that governs redox reactions. This study shows the role played by the silicate network polymerization on the redox kinetics. In borosilicate melts, iron redox kinetics depends on the boron speciation between BO 3 and BO 4 that depends itself on the sodium content. Furthermore, an increase in the network-former/network-modifier ratio implies a decrease in oxygen diffusion that results in a slowing down of the redox kinetics. The obtained results allow a description of the iron redox kinetics for more complex compositions as natural lavas or nuclear waste model glasses. (author)

Redox homeostasis: The Golden Mean of healthy living.

Science.gov (United States)

Ursini, Fulvio; Maiorino, Matilde; Forman, Henry Jay

2016-08-01

The notion that electrophiles serve as messengers in cell signaling is now widely accepted. Nonetheless, major issues restrain acceptance of redox homeostasis and redox signaling as components of maintenance of a normal physiological steady state. The first is that redox signaling requires sudden switching on of oxidant production and bypassing of antioxidant mechanisms rather than a continuous process that, like other signaling mechanisms, can be smoothly turned up or down. The second is the misperception that reactions in redox signaling involve "reactive oxygen species" rather than reaction of specific electrophiles with specific protein thiolates. The third is that hormesis provides protection against oxidants by increasing cellular defense or repair mechanisms rather than by specifically addressing the offset of redox homeostasis. Instead, we propose that both oxidant and antioxidant signaling are main features of redox homeostasis. As the redox shift is rapidly reversed by feedback reactions, homeostasis is maintained by continuous signaling for production and elimination of electrophiles and nucleophiles. Redox homeostasis, which is the maintenance of nucleophilic tone, accounts for a healthy physiological steady state. Electrophiles and nucleophiles are not intrinsically harmful or protective, and redox homeostasis is an essential feature of both the response to challenges and subsequent feedback. While the balance between oxidants and nucleophiles is preserved in redox homeostasis, oxidative stress provokes the establishment of a new radically altered redox steady state. The popular belief that scavenging free radicals by antioxidants has a beneficial effect is wishful thinking. We propose, instead, that continuous feedback preserves nucleophilic tone and that this is supported by redox active nutritional phytochemicals. These nonessential compounds, by activating Nrf2, mimic the effect of endogenously produced electrophiles (parahormesis). In summary

Characterisation and application of the Fe(II)/Fe(III) redox reaction in an ionic liquid analogue

International Nuclear Information System (INIS)

Lloyd, David; Vainikka, Tuomas; Ronkainen, Markus; Kontturi, Kyösti

2013-01-01

Highlights: • The Fe(II)/Fe(III) reaction is shown to be facile using a wall-jet electrode and RDE. • Deposition/stripping of iron has equally slow kinetics as in aqueous systems. • An IL based all-iron RFB is reported for the first time, energy efficiency is 37%. • An Zn–Fe complex is shown to form. In an RFB this gives an energy efficiency of 78%. • Problems resulting from the use of redox probes and urea-based DES are demonstrated. -- Abstract: In this paper we report the properties of the Fe(II)/Fe(III) reaction in a deep eutectic solvent based on choline chloride and ethylene glycol. This reaction is shown to be facile using a wall-jet electrode and rotating disc electrode. The deposition and stripping of iron exhibits equally slow kinetics as in aqueous systems. Using these two reactions an all-iron redox flow battery based on ionic liquids is reported for the first time. An energy efficiency of 37% is attained at a current density of 0.5 mA cm −2 . A Zn(II)–Fe(II) complex is shown to form when zinc is oxidized by Fe(III). When this complex is applied in a redox flow battery energy efficiencies of 78% are achieved at a current density of 0.5 mA cm −2

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.

Efficiency improvement of an all-vanadium redox flow battery by harvesting low-grade heat

Science.gov (United States)

Reynard, Danick; Dennison, C. R.; Battistel, Alberto; Girault, Hubert H.

2018-06-01

Redox flow batteries (RFBs) are rugged systems, which can withstand several thousand cycles and last many years. However, they suffer from low energy density, low power density, and low efficiency. Integrating a Thermally Regenerative Electrochemical Cycle (TREC) into the RFB, it is possible to mitigate some of these drawbacks. The TREC takes advantage of the temperature dependence of the cell voltage to convert heat directly into electrical energy. Here, the performance increase of a TREC-RFB is investigated using two kinds of all-vanadium electrolyte chemistries: one containing a typical concentration of sulfuric acid and one containing a large excess of hydrochloric acid. The results show that the energy density of the system was increased by 1.3Wh L-1 and 0.8Wh L-1, respectively and the overall energy efficiency also increased by 9 and 5 percentage points, respectively. The integration of the heat exchangers necessary to change the battery temperature is readily facilitated by the design of the redox flow battery, which already utilizes fluid circulation loops.

Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries

Science.gov (United States)

Assat, Gaurav; Tarascon, Jean-Marie

2018-05-01

Our increasing dependence on lithium-ion batteries for energy storage calls for continual improvements in the performance of their positive electrodes, which have so far relied solely on cationic redox of transition-metal ions for driving the electrochemical reactions. Great hopes have recently been placed on the emergence of anionic redox—a transformational approach for designing positive electrodes as it leads to a near-doubling of capacity. But questions have been raised about the fundamental origins of anionic redox and whether its full potential can be realized in applications. In this Review, we discuss the underlying science that triggers a reversible and stable anionic redox activity. Furthermore, we highlight its practical limitations and outline possible approaches for improving such materials and designing new ones. We also summarize their chances for market implementation in the face of the competing nickel-based layered cathodes that are prevalent today.

Fabrication of Fe1.1Se0.5Te0.5 bulk by a high energy ball milling technique

Science.gov (United States)

Liu, Jixing; Li, Chengshan; Zhang, Shengnan; Feng, Jianqing; Zhang, Pingxiang; Zhou, Lian

2017-11-01

Fe1.1Se0.5Te0.5 superconducting bulks were successfully synthesized by a high energy ball milling (HEBM) aided sintering technique. Two advantages of this new technique have been revealed compared with traditional solid state sintering method. One is greatly increased the density of sintered bulks. It is because the precursor powders with β-Fe(Se, Te) and δ-Fe(Se, Te) were obtained directly by the HEBM process and without formation of liquid Se (and Te), which could avoid the huge volume expansion. The other is the obvious decrease of sintering temperature and dwell time due to the effective shortened length of diffusion paths. The superconducting critical temperature Tc of 14.2 K in our sample is comparable with those in previous reports, and further optimization of chemical composition is on the way.

Discrete redox signaling pathways regulate photosynthetic light-harvesting and chloroplast gene transcription.

Directory of Open Access Journals (Sweden)

John F Allen

Full Text Available In photosynthesis in chloroplasts, two related regulatory processes balance the actions of photosystems I and II. These processes are short-term, post-translational redistribution of light-harvesting capacity, and long-term adjustment of photosystem stoichiometry initiated by control of chloroplast DNA transcription. Both responses are initiated by changes in the redox state of the electron carrier, plastoquinone, which connects the two photosystems. Chloroplast Sensor Kinase (CSK is a regulator of transcription of chloroplast genes for reaction centres of the two photosystems, and a sensor of plastoquinone redox state. We asked whether CSK is also involved in regulation of absorbed light energy distribution by phosphorylation of light-harvesting complex II (LHC II. Chloroplast thylakoid membranes isolated from a CSK T-DNA insertion mutant and from wild-type Arabidopsis thaliana exhibit similar light- and redox-induced (32P-labelling of LHC II and changes in 77 K chlorophyll fluorescence emission spectra, while room-temperature chlorophyll fluorescence emission transients from Arabidopsis leaves are perturbed by inactivation of CSK. The results indicate indirect, pleiotropic effects of reaction centre gene transcription on regulation of photosynthetic light-harvesting in vivo. A single, direct redox signal is transmitted separately to discrete transcriptional and post-translational branches of an integrated cytoplasmic regulatory system.

Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox

Science.gov (United States)

Zhan, Chun; Yao, Zhenpeng; Lu, Jun; Ma, Lu; Maroni, Victor A.; Li, Liang; Lee, Eungje; Alp, Esen E.; Wu, Tianpin; Wen, Jianguo; Ren, Yang; Johnson, Christopher; Thackeray, Michael M.; Chan, Maria K. Y.; Wolverton, Chris; Amine, Khalil

2017-12-01

Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2- is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Moreover, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.

Polymer-Polymer Förster Resonance Energy Transfer Significantly Boosts the Power Conversion Efficiency of Bulk-Heterojunction Solar Cells.

Science.gov (United States)

Gupta, Vinay; Bharti, Vishal; Kumar, Mahesh; Chand, Suresh; Heeger, Alan J

2015-08-01

Optically resonant donor polymers can exploit a wider range of the solar spectrum effectively without a complicated tandem design in an organic solar cell. Ultrafast Förster resonance energy transfer (FRET) in a polymer-polymer system that significantly improves the power conversion efficiency in bulk heterojunction polymer solar cells from 6.8% to 8.9% is demonstrated, thus paving the way to achieving 15% efficient solar cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

Science.gov (United States)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li2Sx electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Neue Elektrolyte zur Steigerung der Energiedichte einer nicht-wässrigen Vanadium-Acetylacetonat-Redox-Flow-Batterie

OpenAIRE

Herr, Tatjana

2015-01-01

Die Redox-Flow-Batterie ist eine vielversprechende Speicherungsmöglichkeit für stationäre Anwendungen. Bei dieser Batterie wird die Energie in einem flüssigen Elektrolyt gespeichert, wobei die Energiedichte von der Konzentration und dem Potentialfenster der gelösten redoxaktiven Substanz abhängt. Zur Steigerung der Energiedichte einer nicht-wässrigen Vanadium-Acetylacetonat-Redox-Flow-Batterie wurden organische Lösungsmittel, welche ein Potentialfenster bis zu 5 V aufweisen, und Lösungsmittel...

Redox characteristics of the eukaryotic cytosol

DEFF Research Database (Denmark)

López-Mirabal, H Reynaldo; Winther, Jakob R

2007-01-01

The eukaryotic cytoplasm has long been regarded as a cellular compartment in which the reduced state of protein cysteines is largely favored. Under normal conditions, the cytosolic low-molecular weight redox buffer, comprising primarily of glutathione, is highly reducing and reactive oxygen species...... (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...... organism, Saccharomyces cerevisiae, where the combination of genetic and biochemical approaches has brought us furthest in understanding the mechanisms underlying cellular redox regulation. It has been shown in yeast that, in addition to the enzyme glutathione reductase, other mechanisms may exist...

Organic non-aqueous cation-based redox flow batteries

Science.gov (United States)

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

2016-03-29

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

Amphoteric Ion-Exchange Membranes with Significantly Improved Vanadium Barrier Properties for All-Vanadium Redox Flow Batteries.

Science.gov (United States)

Nibel, Olga; Rojek, Tomasz; Schmidt, Thomas J; Gubler, Lorenz

2017-07-10

All-vanadium redox flow batteries (VRBs) have attracted considerable interest as promising energy-storage devices that can allow the efficient utilization of renewable energy sources. The membrane, which separates the porous electrodes in a redox flow cell, is one of the key components in VRBs. High rates of crossover of vanadium ions and water through the membrane impair the efficiency and capacity of a VRB. Thus, membranes with low permeation rate of vanadium species and water are required, also characterized by low resistance and stability in the VRB environment. Here, we present a new design concept for amphoteric ion-exchange membranes, based on radiation-induced grafting of vinylpyridine into an ethylene tetrafluoroethylene base film and a two-step functionalization to introduce cationic and anionic exchange sites, respectively. During long-term cycling, redox flow cells containing these membranes showed higher efficiency, less pronounced electrolyte imbalance, and significantly reduced capacity decay compared to the cells with the benchmark material Nafion 117. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Delocalization of brane gravity by a bulk black hole

International Nuclear Information System (INIS)

Seahra, Sanjeev S; Clarkson, Chris; Maartens, Roy

2005-01-01

We investigate the analogue of the Randall-Sundrum braneworld in the case when the bulk contains a black hole. Instead of the static vacuum Minkowski brane of the RS model, we have an Einstein static vacuum brane. We find that the presence of the bulk black hole has a dramatic effect on the gravity that is felt by brane observers. In the RS model, the 5D graviton has a stable localized zero mode that reproduces 4D gravity on the brane at low energies. With a bulk black hole, there is no such solution-gravity is delocalized by the 5D horizon. However, the brane does support a discrete spectrum of metastable massive bound states, or quasinormal modes, as was recently shown to be the case in the RS scenario. These states should dominate the high frequency component of the bulk gravity wave spectrum on a cosmological brane. We expect our results to generalize to any bulk spacetime containing a Killing horizon. (letter to the editor)

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

Energy Technology Data Exchange (ETDEWEB)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li₂S_x electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Redox regulation of plant development.

Science.gov (United States)

Considine, Michael J; Foyer, Christine H

2014-09-20

We provide a conceptual framework for the interactions between the cellular redox signaling hub and the phytohormone signaling network that controls plant growth and development to maximize plant productivity under stress-free situations, while limiting growth and altering development on exposure to stress. Enhanced cellular oxidation plays a key role in the regulation of plant growth and stress responses. Oxidative signals or cycles of oxidation and reduction are crucial for the alleviation of dormancy and quiescence, activating the cell cycle and triggering genetic and epigenetic control that underpin growth and differentiation responses to changing environmental conditions. The redox signaling hub interfaces directly with the phytohormone network in the synergistic control of growth and its modulation in response to environmental stress, but a few components have been identified. Accumulating evidence points to a complex interplay of phytohormone and redox controls that operate at multiple levels. For simplicity, we focus here on redox-dependent processes that control root growth and development and bud burst. The multiple roles of reactive oxygen species in the control of plant growth and development have been identified, but increasing emphasis should now be placed on the functions of redox-regulated proteins, along with the central roles of reductants such as NAD(P)H, thioredoxins, glutathione, glutaredoxins, peroxiredoxins, ascorbate, and reduced ferredoxin in the regulation of the genetic and epigenetic factors that modulate the growth and vigor of crop plants, particularly within an agricultural context.

Bulk electronic state of high-Tc cuprate La2-xSrxCuO4 observed by high-energy angle integrated and resolved photoemission spectroscopy

International Nuclear Information System (INIS)

Kasai, S.; Sekiyama, A.; Tsunekawa, M.; Ernst, P.T.; Shigemoto, A.; Yamasaki, A.; Irizawa, A.; Imada, S.; Sing, M.; Muro, T.; Sasagawa, T.; Takagi, H.; Suga, S.

2005-01-01

The high-energy core-level photoemission spectroscopy (PES) and angle-resolved photoemission spectroscopy (ARPES) measurements have been performed for La 2-x Sr x CuO 4 (LSCO). Polar-angle dependence of the Cu 2p core-level PES has revealed a discrepancy between bulk and surface. We have observed by the high-energy ARPES that the Fermi surface of LSCO with x=0.16 is electron-like, in contrast to previous low-energy ARPES results

Bulk density calculations from prompt gamma ray yield

International Nuclear Information System (INIS)

Naqvi, A.A.; Nagadi, M.M.; Al-Amoudi, O.S.B.; Maslehuddin, M.

2006-01-01

Full text: The gamma ray yield from a Prompt Gamma ray Neutron Activation Analysis (PGNAA) setup is a linear function of element concentration and neutron flux in a the sample with constant bulk density. If the sample bulk density varies as well, then the element concentration and the neutron flux has a nonlinear correlation with the gamma ray yield [1]. The measurement of gamma ray yield non-linearity from samples and a standard can be used to estimate the bulk density of the samples. In this study the prompt gamma ray yield from Blast Furnace Slag, Fly Ash, Silica Fumes and Superpozz cements samples have been measured as a function of their calcium and silicon concentration using KFUPM accelerator-based PGNAA setup [2]. Due to different bulk densities of the blended cement samples, the measured gamma ray yields have nonlinear correlation with calcium and silicon concentration of the samples. The non-linearity in the yield was observed to increase with gamma rays energy and element concentration. The bulk densities of the cement samples were calculated from ratio of gamma ray yield from blended cement and that from a Portland cement standard. The calculated bulk densities have good agreement with the published data. The result of this study will be presented

Coordinated Control of Distributed and Bulk Energy Storage for Alleviation of Post-Contingency Overloads

Directory of Open Access Journals (Sweden)

Yunfeng Wen

2014-03-01

Full Text Available This paper presents a novel corrective control strategy that can effectively coordinate distributed and bulk energy storage to relieve post-contingency overloads. Immediately following a contingency, distributed batteries are implemented to provide fast corrective actions to reduce power flows below their short-term emergency ratings. During the long-term period, Pumped Hydro Storage units work in pumping or generation mode to aid conventional generating units keep line flows below the normal ratings. This problem is formulated as a multi-stage Corrective Security-constrained OPF (CSCOPF. An algorithm based on Benders decomposition was proposed to find the optimal base case solution and seek feasible corrective actions to handle all contingencies. Case studies based on a modified RTS-96 system demonstrate the performance and effectiveness of the proposed control strategy.

High-pressure X-ray diffraction study of bulk- and nanocrystalline GaN

DEFF Research Database (Denmark)

Jorgensen, J.E.; Jakobsen, J.M.; Jiang, Jianzhong

2003-01-01

Bulk- and nanocrystalline GaN have been studied by high-pressure energy-dispersive X-ray diffraction. Pressure-induced structural phase transitions from the wurtzite to the NaCl phase were observed in both materials. The transition pressure was found to be 40 GPa for the bulk-crystalline GaN, while...... the wurtzite phase was retained up to 60 GPa in the case of nanocrystalline GaN. The bulk moduli for the wurtzite phases were determined to be 187 ( 7) and 319 ( 10) GPa for the bulk- and nanocrystalline phases, respectively, while the respective NaCl phases were found to have very similar bulk moduli [ 208...

Iron Redox Dynamics in Humid Tropical Forest Soils: Carbon Stabilization vs. Degradation?

Science.gov (United States)

Hall, S. J.; Silver, W. L.; Hammel, K.

2015-12-01

Most terrestrial soils exhibit a patchwork of oxygen (O2) availability that varies over spatial scales of microsites to catenas to landscapes, and over temporal scales of minutes to seasons. Oxygen fluctuations often drive microbial iron (Fe) reduction and abiotic/biotic Fe oxidation at the microsite scale, contributing to anaerobic carbon (C) mineralization and changes in soil physical and chemical characteristics, especially the dissolution and precipitation of short-range ordered Fe phases thought to stabilize C. Thus, O2 fluctuations and Fe redox cycling may have multiple nuanced and opposing impacts on different soil C pools, illustrated by recent findings from Fe-rich Oxisols and Ultisols in the Luquillo Experimental Forest, Puerto Rico. Spatial patterns in surface soil C stocks at the landscape scale correlated strongly (R2 = 0.98) with concentrations of reduced Fe (Fe(II)), reflecting constitutive differences in reducing conditions within and among sites that promote C accumulation in mineral soil horizons. Similarly, turnover times of a decadal-cycling pool of mineral-associated organic matter increased with Fe(II) across a catena, possibly reflecting the role of anaerobic microsites in long-term C stabilization. However, two different indices of short-range order Fe showed highly significant opposing relationships (positive and negative) with spatial variation in soil C concentrations, possibly reflecting a dual role of Fe in driving C stabilization via co-precipitation, and C solubilization and loss following dissimilatory Fe reduction. Consistent with the field data, laboratory incubations demonstrated that redox fluctuations can increase the contribution of biochemically recalcitrant C (lignin) to soil respiration, whereas addition of short-range order Fe dramatically suppressed lignin mineralization but had no impact on bulk soil respiration. Thus, understanding spatial and temporal patterns of Fe redox cycling may provide insight into explaining the

Palladium diffusion into bulk copper via the (100) surface

Energy Technology Data Exchange (ETDEWEB)

Bussmann, E; Kellogg, G L [Sandia National Laboratories, Albuquerque, NM 87185 (United States); Sun, J; Pohl, K [Department of Physics and Materials Science Program, University of New Hampshire, Durham, NH 03824 (United States)

2009-08-05

Using low-energy electron microscopy, we measure the diffusion of Pd into bulk Cu at the Cu(100) surface. Interdiffusion is tracked by measuring the dissolution of the Cu(100)-c(2 x 2)-Pd surface alloy during annealing (T>240 deg. C). The activation barrier for Pd diffusion from the surface alloy into the bulk is determined to be (1.8 +- 0.6) eV. During annealing, we observe the growth of a new layer of Cu near step edges. Under this new Cu layer, dilute Pd remaining near the surface develops a layered structure similar to the Cu{sub 3}Pd L 1{sub 2} bulk alloy phase.

Reversible ultrafast melting in bulk CdSe

International Nuclear Information System (INIS)

Wu, Wenzhi; He, Feng; Wang, Yaguo

2016-01-01

In this work, transient reflectivity changes in bulk CdSe have been measured with two-color femtosecond pump-probe spectroscopy under a wide range of pump fluences. Three regions of reflectivity change with pump fluences have been consistently revealed for excited carrier density, coherent phonon amplitude, and lattice temperature. For laser fluences from 13 to 19.3 mJ/cm 2 , ultrafast melting happens in first several picoseconds. This melting process is purely thermal and reversible. A complete phase transformation in bulk CdSe may be reached when the absorbed laser energy is localized long enough, as observed in nanocrystalline CdSe

How High Local Charge Carrier Mobility and an Energy Cascade in a Three-Phase Bulk Heterojunction Enable >90% Quantum Efficiency

KAUST Repository

Burke, Timothy M.

2013-12-27

Charge generation in champion organic solar cells is highly efficient in spite of low bulk charge-carrier mobilities and short geminate-pair lifetimes. In this work, kinetic Monte Carlo simulations are used to understand efficient charge generation in terms of experimentally measured high local charge-carrier mobilities and energy cascades due to molecular mixing. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

How High Local Charge Carrier Mobility and an Energy Cascade in a Three-Phase Bulk Heterojunction Enable >90% Quantum Efficiency

KAUST Repository

Burke, Timothy M.; McGehee, Michael D.

2013-01-01

Charge generation in champion organic solar cells is highly efficient in spite of low bulk charge-carrier mobilities and short geminate-pair lifetimes. In this work, kinetic Monte Carlo simulations are used to understand efficient charge generation in terms of experimentally measured high local charge-carrier mobilities and energy cascades due to molecular mixing. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bulk GaN alpha-particle detector with large depletion region and improved energy resolution

Science.gov (United States)

Xu, Qiang; Mulligan, Padhraic; Wang, Jinghui; Chuirazzi, William; Cao, Lei

2017-03-01

An alpha-particle detector was fabricated using a freestanding n-type bulk GaN wafer with a Au/Ni/GaN sandwich Schottky structure. Current-voltage measurements at room temperature revealed a Schottky contact with a leakage current of 7.53±0.3 nA at a reverse bias of 200 V. The detector had a large depletion depth that can capture much of the energy from 5.486 MeV alpha particles emitted from a 241Am source. The resolution of its alpha-particle energy spectrum was improved to 2.2±0.2% at 5.486 MeV under a bias of 550 V. This superior resolution was attributed to the shortening of the carrier transit time and the large energy deposition within the large depletion depth, i.e., 27 μm at -550 V, which all resulted in a more complete charge collection. A model developed using the ATLAS simulation framework from Silvaco Inc. was employed to study the charge collection process. The simulation results were found to agree closely with the experimental results. This detector will be beneficial for research at neutron scattering facilities, the International Thermonuclear Experimental Reactor, and the Large Hadron Collider, among other institutions, where the Si-based charged particle detectors could be quickly degraded in an intense radiation field.

High temperature superconductor bulk materials. Fundamentals - processing - properties control - application aspects

International Nuclear Information System (INIS)

Krabbes, G.; Fuchs, G.; Canders, W.R.; May, H.; Palka, R.

2006-01-01

This book presents all the features of bulk high temperature superconducting materials. Starting from physical and chemical fundamentals, the authors move on to portray methods and problems of materials processing, thoroughly working out the characteristic properties of bulk superconductors in contrast to long conductors and films. The authors provide a wide range of specific materials characteristics with respect to the latest developments and future applications guiding from fundamentals to practical engineering examples. This book contains the following chapters: 1. Fundamentals 2. Growth and melt processing of YBCO 3. Pinning-relevant defects in bulk YBCO 4. Properties of bulk YBCO 5. Trapped fields 6. Improved YBCO based bulk superconductors and functional elements 7. Alternative systems 8. Peak effect 9. Very high trapped fields in YBCO permanent magnets 10. Engineering aspects: Field distribution in bulk HTSC 11. Inherently stable superconducting magnetic bearings 12. Application of bulk HTSCs in electromagnetic energy converters 13. Applications in magnet technologies and power supplies

Monitoring thioredoxin redox with a genetically encoded red fluorescent biosensor.

Science.gov (United States)

Fan, Yichong; Makar, Merna; Wang, Michael X; Ai, Hui-Wang

2017-09-01

Thioredoxin (Trx) is one of the two major thiol antioxidants, playing essential roles in redox homeostasis and signaling. Despite its importance, there is a lack of methods for monitoring Trx redox dynamics in live cells, hindering a better understanding of physiological and pathological roles of the Trx redox system. In this work, we developed the first genetically encoded fluorescent biosensor for Trx redox by engineering a redox relay between the active-site cysteines of human Trx1 and rxRFP1, a redox-sensitive red fluorescent protein. We used the resultant biosensor-TrxRFP1-to selectively monitor perturbations of Trx redox in various mammalian cell lines. We subcellularly localized TrxRFP1 to image compartmentalized Trx redox changes. We further combined TrxRFP1 with a green fluorescent Grx1-roGFP2 biosensor to simultaneously monitor Trx and glutathione redox dynamics in live cells in response to chemical and physiologically relevant stimuli.

ETL 1 kW redox flow cell

International Nuclear Information System (INIS)

Nozaki, K.; Ozawa, T.

1984-01-01

A 1 kW scale redox flow cell system was set up in the laboratory (ETL), while three different types of batteries were also assembled by private companies in early 1983. In this article, this cell system is described. The concept of a modern type redox flow cell is based on a couple of fully soluble redox ions and a highly selective ion-exchange membrane. In the cell, the redox ion stored in a tank is flowed to and reduced on the electrode, while the other ion is also flowed to and oxidized on the other electrode. This electrochemical reaction produces electronic current in the external circuit and ionic current through the membrane sandwiched as a separator between the two electrodes. The reverse reaction proceeds in the charging process. In ETL, the concept was preliminarily tested, and conceptual design and cost estimation of the redox flow cells were carried out to confirm the feasibility; the R and D started on these bases in 1975

Running with rugby balls: bulk renormalization of codimension-2 branes

Science.gov (United States)

Williams, M.; Burgess, C. P.; van Nierop, L.; Salvio, A.

2013-01-01

We compute how one-loop bulk effects renormalize both bulk and brane effective interactions for geometries sourced by codimension-two branes. We do so by explicitly integrating out spin-zero, -half and -one particles in 6-dimensional Einstein-Maxwell-Scalar theories compactified to 4 dimensions on a flux-stabilized 2D geometry. (Our methods apply equally well for D dimensions compactified to D - 2 dimensions, although our explicit formulae do not capture all divergences when D > 6.) The renormalization of bulk interactions are independent of the boundary conditions assumed at the brane locations, and reproduce standard heat-kernel calculations. Boundary conditions at any particular brane do affect how bulk loops renormalize this brane's effective action, but not the renormalization of other distant branes. Although we explicitly compute our loops using a rugby ball geometry, because we follow only UV effects our results apply more generally to any geometry containing codimension-two sources with conical singularities. Our results have a variety of uses, including calculating the UV sensitivity of one-loop vacuum energy seen by observers localized on the brane. We show how these one-loop effects combine in a surprising way with bulk back-reaction to give the complete low-energy effective cosmological constant, and comment on the relevance of this calculation to proposed applications of codimension-two 6D models to solutions of the hierarchy and cosmological constant problems.

Faradic redox active material of Cu7S4 nanowires with a high conductance for flexible solid state supercapacitors

Science.gov (United States)

Javed, Muhammad Sufyan; Dai, Shuge; Wang, Mingjun; Xi, Yi; Lang, Qiang; Guo, Donglin; Hu, Chenguo

2015-08-01

The exploration of high Faradic redox active materials with the advantages of low cost and low toxicity has been attracting great attention for producing high energy storage supercapacitors. Here, the high Faradic redox active material of Cu7S4-NWs coated on a carbon fiber fabric (CFF) is directly used as a binder-free electrode for a high performance flexible solid state supercapacitor. The Cu7S4-NW-CFF supercapacitor exhibits excellent electrochemical performance such as a high specific capacitance of 400 F g-1 at the scan rate of 10 mV s-1 and a high energy density of 35 Wh kg-1 at a power density of 200 W kg-1, with the advantages of a light weight, high flexibility and long term cycling stability by retaining 95% after 5000 charge-discharge cycles at a constant current of 10 mA. The high Faradic redox activity and high conductance behavior of the Cu7S4-NWs result in a high pseudocapacitive performance with a relatively high specific energy and specific power. Such a new type of pseudocapacitive material of Cu7S4-NWs with its low cost is very promising for actual application in supercapacitors.The exploration of high Faradic redox active materials with the advantages of low cost and low toxicity has been attracting great attention for producing high energy storage supercapacitors. Here, the high Faradic redox active material of Cu7S4-NWs coated on a carbon fiber fabric (CFF) is directly used as a binder-free electrode for a high performance flexible solid state supercapacitor. The Cu7S4-NW-CFF supercapacitor exhibits excellent electrochemical performance such as a high specific capacitance of 400 F g-1 at the scan rate of 10 mV s-1 and a high energy density of 35 Wh kg-1 at a power density of 200 W kg-1, with the advantages of a light weight, high flexibility and long term cycling stability by retaining 95% after 5000 charge-discharge cycles at a constant current of 10 mA. The high Faradic redox activity and high conductance behavior of the Cu7S4-NWs result in

Mn3O4 anchored on carbon nanotubes as an electrode reaction catalyst of V(IV)/V(V) couple for vanadium redox flow batteries

International Nuclear Information System (INIS)

He, Zhangxing; Dai, Lei; Liu, Suqin; Wang, Ling; Li, Chuanchang

2015-01-01

Highlights: • Mn 3 O 4 /MWCNTs (multi-walled carbon nanotubes) composite fabricated by a simple solvothermal method was developed as electrochemical catalyst of V(IV)/V(V) redox couple for vanadium redox flow batteries for the first time. • The electrocatalytic kinetics of the redox reactions of three electrocatalysts (pure Mn 3 O 4 , pure MWCNTs, Mn 3 O 4 /MWCNTs) were compared, and were in the order of Mn 3 O 4 /MWCNTs > MWCNTs > Mn 3 O 4 . • The cell using Mn 3 O 4 /MWCNTs has lower electrochemical polarization, with larger discharge capacity and energy efficiency. The average energy efficiency of the cell using Mn 3 O 4 /MWCNTs is 84.65%, 3.73% higher than that of the pristine cell. - Abstract: Mn 3 O 4 /MWCNTs (multi-walled carbon nanotubes) composite fabricated by a simple solvothermal method was developed as electrochemical catalyst of V(IV)/V(V) redox couple for vanadium redox flow batteries. The electrochemical activity of V(IV)/V(V) redox couple can be enhanced by the electrochemical catalysts (Mn 3 O 4 , MWCNTs, Mn 3 O 4 /MWCNTs), and the electrocatalytic kinetics of the redox reactions were in the order of Mn 3 O 4 /MWCNTs > MWCNTs > Mn 3 O 4 . The cell using Mn 3 O 4 /MWCNTs composite as electrochemical catalyst was assembled and the charge-discharge performance was evaluated. Compared with the pristine cell, the cell using positive graphite felt modified by Mn 3 O 4 /MWCNTs had lower electrochemical polarization, larger discharge capacity and energy efficiency. The average energy efficiency of the cell using modified positive electrode for 50 cycles was 84.65%, 3.73% higher than that of the pristine cell. The superior electrocatalytic performance of Mn 3 O 4 /MWCNTs composite was mainly due to the effective mixed conducting network, facilitating the electron transport and ion diffusion in the electrode/electrolyte interface

Subcellular Redox Targeting: Bridging in Vitro and in Vivo Chemical Biology.

Science.gov (United States)

Long, Marcus J C; Poganik, Jesse R; Ghosh, Souradyuti; Aye, Yimon

2017-03-17

Networks of redox sensor proteins within discrete microdomains regulate the flow of redox signaling. Yet, the inherent reactivity of redox signals complicates the study of specific redox events and pathways by traditional methods. Herein, we review designer chemistries capable of measuring flux and/or mimicking subcellular redox signaling at the cellular and organismal level. Such efforts have begun to decipher the logic underlying organelle-, site-, and target-specific redox signaling in vitro and in vivo. These data highlight chemical biology as a perfect gateway to interrogate how nature choreographs subcellular redox chemistry to drive precision redox biology.

Density-functional molecular-dynamics study of the redox reactions of two anionic, aqueous transition-metal complexes

International Nuclear Information System (INIS)

Tateyama, Yoshitaka; Blumberger, Jochen; Sprik, Michiel; Tavernelli, Ivano

2005-01-01

The thermochemistry of the RuO 4 2- +MnO 4 - →RuO 4 - +MnO 4 2- redox reaction in aqueous solution is studied by separate density-functional-based ab initio molecular-dynamics simulations of the component half reactions RuO 4 2- →RuO 4 - +e - and MnO 4 2- →MnO 4 - +e - . We compare the results of a recently developed grand-canonical method for the computation of oxidation free energies to the predictions by the energy-gap relations of the Marcus theory that can be assumed to apply to these reactions. The calculated redox potentials are in good agreement. The subtraction of the half-reaction free energies gives an estimate of the free energy of the full reaction. The result obtained from the grand-canonical method is -0.4 eV, while the application of the Marcus theory gives -0.3 eV. These should be compared to the experimental value of 0.0 eV. Size effects, in response to increasing the number of water molecules in the periodic model system from 30 to 48, are found to be small (≅0.1 eV). The link to the Marcus theory also has enabled us to compute reorganization free energies for oxidation. For both the MnO 4 2- and RuO 4 2- redox reactions we find the same reorganization free energy of 0.8 eV (1.0 eV in the larger system). The results for the free energies and further analysis of solvation and electronic structure confirm that these two tetrahedral oxoanions show very similar behavior in solution in spite of the central transition-metal atoms occupying a different row and column in the periodic table

A High-Current, Stable Nonaqueous Organic Redox Flow Battery

Energy Technology Data Exchange (ETDEWEB)

Wei, Xiaoliang; Duan, Wentao; Huang, Jinhua; Zhang, Lu; Li, Bin; Reed, David; Xu, Wu; Sprenkle, Vincent; Wang, Wei

2016-10-14

Nonaqueous redox flow batteries are promising in pursuit of high-energy storage systems owing to the broad voltage window, but currently are facing key challenges such as poor cycling stability and lack of suitable membranes. Here we report a new nonaqueous all-organic flow chemistry that demonstrates an outstanding cell cycling stability primarily because of high chemical persistency of the organic radical redox species and their good compatibility with the supporting electrolyte. A feasibility study shows that Daramic® and Celgard® porous separators can lead to high cell conductivity in flow cells thus producing remarkable cell efficiency and material utilization even at high current operations. This result suggests that the thickness and pore size are the key performance-determining factors for porous separators. With the greatly improved flow cell performance, this new flow system largely addresses the above mentioned challenges and the findings may greatly expedite the development of durable nonaqueous flow batteries.

Neutral Red and Ferroin as Reversible and Rapid Redox Materials for Redox Flow Batteries.

Science.gov (United States)

Hong, Jeehoon; Kim, Ketack

2018-04-17

Neutral red and ferroin are used as redox indicators (RINs) in potentiometric titrations. The rapid response and reversibility that are prerequisites for RINs are also desirable properties for the active materials in redox flow batteries (RFBs). This study describes the electrochemical properties of ferroin and neutral red as a redox pair. The rapid reaction rates of the RINs allow a cell to run at a rate of 4 C with 89 % capacity retention after the 100 th  cycle. The diffusion coefficients, electrode reaction rates, and solubilities of the RINs were determined. The electron-transfer rate constants of ferroin and neutral red are 0.11 and 0.027 cm s -1 , respectively, which are greater than those of the components of all-vanadium and Zn/Br 2 cells. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry.

Science.gov (United States)

Lu, Ke; Hu, Ziyu; Ma, Jizhen; Ma, Houyi; Dai, Liming; Zhang, Jintao

2017-09-13

Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine-carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance.Carbon-based electrodes able to intercalate Li + and Na + ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine-carbon batteries with high reversible capacities.

Redox shuttles for safer lithium-ion batteries

International Nuclear Information System (INIS)

Chen, Zonghai; Qin, Yan; Amine, Khalil

2009-01-01

Overcharge protection is not only critical for preventing the thermal runaway of lithium-ion batteries during operation, but also important for automatic capacity balancing during battery manufacturing and repair. A redox shuttle is an electrolyte additive that can be used as intrinsic overcharge protection mechanism to enhance the safety characteristics of lithium-ion batteries. The advances on stable redox shuttles are briefly reviewed. Fundamental studies for designing stable redox shuttles are also discussed.

Microfluidic redox battery.

Science.gov (United States)

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

2013-07-07

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.

Enhancing Capacity Performance by Utilizing the Redox Chemistry of the Electrolyte in a Dual-Electrolyte Sodium-Ion Battery.

Science.gov (United States)

Senthilkumar, Sirugaloor Thangavel; Bae, Hyuntae; Han, Jinhyup; Kim, Youngsik

2018-05-04

A strategy is described to increase charge storage in a dual electrolyte Na-ion battery (DESIB) by combining the redox chemistry of the electrolyte with a Na + ion de-insertion/insertion cathode. Conventional electrolytes do not contribute to charge storage in battery systems, but redox-active electrolytes augment this property via charge transfer reactions at the electrode-electrolyte interface. The capacity of the cathode combined with that provided by the electrolyte redox reaction thus increases overall charge storage. An aqueous sodium hexacyanoferrate (Na 4 Fe(CN) 6 ) solution is employed as the redox-active electrolyte (Na-FC) and sodium nickel Prussian blue (Na x -NiBP) as the Na + ion insertion/de-insertion cathode. The capacity of DESIB with Na-FC electrolyte is twice that of a battery using a conventional (Na 2 SO 4 ) electrolyte. The use of redox-active electrolytes in batteries of any kind is an efficient and scalable approach to develop advanced high-energy-density storage systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox reactions in micellar systems. communication 4. Eosin-photosensitized reduction of methylviologen

Energy Technology Data Exchange (ETDEWEB)

Nadtochenko, V.; Dzhabiev, T.S.; Rubtsov, I.V.

1985-12-10

The authors present data on photosensitized reduction of methylviologen (MV/sup 2 +/) by disodium ethylenediaminetetraacetate (EDTA) in micellar systems modeling, in a first approximation, the structural organization of components of the chain of energy and electron transfer in natural photosynthesis. Photosensitized reduction of methylviologen by EDTA in micellar solutions can model photosystem I of plants with structure formation of reagents and transfer of excitation energy before the step of occurrence of a redox reaction in the active center.

Ultraviolet photoelectron spectroscopy reveals energy-band dispersion for π-stacked 7,8,15,16-tetraazaterrylene thin films in a donor–acceptor bulk heterojunction

Science.gov (United States)

Aghdassi, Nabi; Wang, Qi; Ji, Ru-Ru; Wang, Bin; Fan, Jian; Duhm, Steffen

2018-05-01

7,8,15,16-tetraazaterrylene (TAT) thin films grown on highly oriented pyrolytic graphite (HOPG) substrates were studied extensively with regard to their intrinsic and interfacial electronic properties by means of ultraviolet photoelectron spectroscopy (UPS). Merely weak substrate–adsorbate interaction occurs at the TAT/HOPG interface, with interface energetics being only little affected by the nominal film thickness. Photon energy-dependent UPS performed perpendicular to the molecular planes of TAT multilayer films at room temperature clearly reveals band-like intermolecular dispersion of the TAT highest occupied molecular orbital (HOMO) energy. Based on a comparison with a tight-binding model, a relatively narrow bandwidth of 54 meV is derived, which points to the presence of an intermediate regime between hopping and band-like hole transport. Upon additional deposition of 2,2‧:5‧,2″:5″,2″‧-quaterthiophene (4T), a 4T:TAT donor–acceptor bulk heterojunction with a considerable HOMO-level offset at the donor–acceptor interface is formed. The 4T:TAT bulk heterojunction likewise exhibits intermolecular dispersion of the TAT HOMO energy, yet with a significant decreased bandwidth.

Unusual thiol-based redox metabolism of parasitic flukes.

Science.gov (United States)

Tripathi, Timir; Suttiprapa, Sutas; Sripa, Banchob

2017-08-01

Parasitic flukes are exposed to free radicals and, to a greater extent, reactive oxygen species (ROS) during their life cycle. Despite being relentlessly exposed to ROS released by activated immune cells, these parasites can survive for many years in the host. Cellular thiol-based redox metabolism plays a crucial role in parasite survival within their hosts. Evidence shows that oxidative stress and redox homeostasis maintenance are important clinical and pathobiochemical as well as effective therapeutic principles in various diseases. The characterization of redox and antioxidant enzymes is likely to yield good target candidates for novel drugs and vaccines. The absence of active catalase in fluke parasites offers great potential for the development of chemotherapeutic agents that act by perturbing the redox equilibrium of the cell. One of the redox-sensitive enzymes, thioredoxin glutathione reductase (TGR), has been accepted as a drug target against blood fluke infections, and related clinical trials are in progress. TGR is the sole enzyme responsible for Trx and GSH reduction in parasitic flukes. The availability of helminth genomes has accelerated the research on redox metabolism of flukes; however, significant achievements have yet to be attained. The present review summarizes current knowledge on the redox and antioxidant system of the parasitic flukes. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

An Accurate Estimate of the Free Energy and Phase Diagram of All-DNA Bulk Fluids

Directory of Open Access Journals (Sweden)

Emanuele Locatelli

2018-04-01

Full Text Available We present a numerical study in which large-scale bulk simulations of self-assembled DNA constructs have been carried out with a realistic coarse-grained model. The investigation aims at obtaining a precise, albeit numerically demanding, estimate of the free energy for such systems. We then, in turn, use these accurate results to validate a recently proposed theoretical approach that builds on a liquid-state theory, the Wertheim theory, to compute the phase diagram of all-DNA fluids. This hybrid theoretical/numerical approach, based on the lowest-order virial expansion and on a nearest-neighbor DNA model, can provide, in an undemanding way, a parameter-free thermodynamic description of DNA associating fluids that is in semi-quantitative agreement with experiments. We show that the predictions of the scheme are as accurate as those obtained with more sophisticated methods. We also demonstrate the flexibility of the approach by incorporating non-trivial additional contributions that go beyond the nearest-neighbor model to compute the DNA hybridization free energy.

Tuning the redox potential of vitamin K3 derivatives by oxidative functionalization using a Ag(i)/GO catalyst.

Science.gov (United States)

El-Hout, S I; Suzuki, H; El-Sheikh, S M; Hassan, H M A; Harraz, F A; Ibrahim, I A; El-Sharkawy, E A; Tsujimura, S; Holzinger, M; Nishina, Y

2017-08-03

We propose herein initial results to develop optimum redox mediators by the combination of computational simulation and catalytic functionalization of the core structure of vitamin K 3 . We aim to correlate the calculated energy value of the LUMO of different vitamin K 3 derivatives with their actual redox potential. For this, we optimized the catalytic alkylation of 1,4-naphthoquinones with a designed Ag(i)/GO catalyst and synthesized a series of molecules.

A non-aqueous all-copper redox flow battery with highly soluble active species

International Nuclear Information System (INIS)

Li, Yun; Sniekers, Jeroen; Malaquias, João; Li, Xianfeng; Schaltin, Stijn; Stappers, Linda; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F.J.

2017-01-01

A metal-based redox pair with acetonitrile as ligand [Cu(MeCN)_4][Tf_2N] is described for use in non-aqueous redox flow battery (RFB). The electrode kinetics of the anode and cathode are studied using cyclic voltammetry. The Cu"2"+/Cu"+ and Cu"+/Cu couples in this system yield a cell potential of 1.24 V. The diffusion coefficient for [Cu(MeCN)_4][Tf_2N] in acetonitrile is estimated to be 6.8 × 10"−"6 cm"2 s"−"1 at room temperature. The copper-acetonitrile complex has a very high solubility of 1.68 M in acetonitrile, the most widely used organic solvent for non-aqueous electrochemical applications. Hence, a maximum theoretical energy density around 28 Wh L"−"1 can be reached with the reported system. The RFB with this electrolyte shows a promising performance, with coulombic efficiencies of 87% and energy efficiencies of 44% (5 mA cm"−"2).

Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

Science.gov (United States)

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

2015-01-01

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

Redox Modulations, Antioxidants, and Neuropsychiatric Disorders

Directory of Open Access Journals (Sweden)

Erik A. Fraunberger

2016-01-01

Full Text Available Although antioxidants, redox modulations, and neuropsychiatric disorders have been widely studied for many years, the field would benefit from an integrative and corroborative review. Our primary objective is to delineate the biological significance of compounds that modulate our redox status (i.e., reactive species and antioxidants as well as outline their current role in brain health and the impact of redox modulations on the severity of illnesses. Therefore, this review will not enter into the debate regarding the perceived medical legitimacy of antioxidants but rather seek to clarify their abilities and limitations. With this in mind, antioxidants may be interpreted as natural products with significant pharmacological actions in the body. A renewed understanding of these often overlooked compounds will allow us to critically appraise the current literature and provide an informed, novel perspective on an important healthcare issue. In this review, we will introduce the complex topics of redox modulations and their role in the development of select neuropsychiatric disorders.

High energy-resolution electron energy-loss spectroscopy study of the dielectric properties of bulk and nanoparticle LaB6 in the near-infrared region

International Nuclear Information System (INIS)

Sato, Yohei; Terauchi, Masami; Mukai, Masaki; Kaneyama, Toshikatsu; Adachi, Kenji

2011-01-01

The dielectric properties of LaB 6 crystals and the plasmonic behavior of LaB 6 nanoparticles, which have been applied to solar heat-shielding filters, were studied by high energy-resolution electron energy-loss spectroscopy (HR-EELS). An EELS spectrum of a LaB 6 crystal showed a peak at 2.0 eV, which was attributed to volume plasmon excitation of carrier electrons. EELS spectra of single LaB 6 nanoparticles showed peaks at 1.1-1.4 eV depending on the dielectric effect from the substrates. The peaks were assigned to dipole oscillation excitations. These peak energies almost coincided with the peak energy of optical absorption of a heat-shielding filter with LaB 6 nanoparticles. On the other hand, those energies were a smaller than a dipole oscillation energy predicted using the dielectric function of bulk LaB 6 crystal. It is suggested that the lower energy than expected is due to an excitation at 1.2 eV, which was observed for oxidized LaB 6 area. -- Highlights: → The dielectric properties of LaB 6 nanoparticles applied to solar heat-shielding filters were studied by HR-EELS. → Plasmon peak energies of the LaB 6 nanoparticles were almost equal to optical absorption energy of a heat-shielding filter. → From this result, near-infrared optical absorption of the filter is due to the surface dipole mode of the nanoparticles.

Measuring intracellular redox conditions using GFP-based sensors

DEFF Research Database (Denmark)

Björnberg, Olof; Ostergaard, Henrik; Winther, Jakob R

2006-01-01

Recent years have seen the development of methods for analyzing the redox conditions in specific compartments in living cells. These methods are based on genetically encoded sensors comprising variants of Green Fluorescent Protein in which vicinal cysteine residues have been introduced at solvent......-exposed positions. Several mutant forms have been identified in which formation of a disulfide bond between these cysteine residues results in changes of their fluorescence properties. The redox sensors have been characterized biochemically and found to behave differently, both spectroscopically and in terms...... of redox properties. As genetically encoded sensors they can be expressed in living cells and used for analysis of intracellular redox conditions; however, which parameters are measured depends on how the sensors interact with various cellular redox components. Results of both biochemical and cell...

Improving the electrocatalytic performance of carbon nanotubes for VO{sup 2+}/VO{sub 2}{sup +} redox reaction by KOH activation

Energy Technology Data Exchange (ETDEWEB)

Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); Wang, Ling, E-mail: tswling@126.com [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); He, Zhangxing, E-mail: zxhe@ncst.edu.cn [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Nanchang 330013 (China)

2017-04-15

Highlights: • KOH-activated carbon nanotubes (CNTs) was investigated as superior catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for vanadium redox flow battery (VRFB) for the first time. • KOH activation for CNTs can result in the chemical etching of surface and improved wettability, accelerating the mass transfer of vanadium ions. • KOH activation can introduce many oxygen-containing groups as active sites on the surface of CNTs. • KOH-activated CNTs as positive catalyst could increase the comprehensive energy storage performance of VRFB. - Abstract: In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO{sup 2+}/VO{sub 2}{sup +} redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO{sup 2+}/VO{sub 2}{sup +} redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for VRFB system.

Development of superconductor bulk for superconductor bearing

Energy Technology Data Exchange (ETDEWEB)

Kim, Chan Joong; Jun, Byung Hyuk; Park, Soon Dong (and others)

2008-08-15

Current carrying capacity is one of the most important issues in the consideration of superconductor bulk materials for engineering applications. There are numerous applications of Y-Ba-Cu-O (YBCO) bulk superconductors e.g. magnetic levitation train, flywheel energy storage system, levitation transportation, lunar telescope, centrifugal device, magnetic shielding materials, bulk magnets etc. Accordingly, to obtain YBCO materials in the form of large, single crystals without weak-link problem is necessary. A top seeded melt growth (TSMG) process was used to fabricate single crystal YBCO bulk superconductors. The seeded and infiltration growth (IG) technique was also very promising method for the synthesis of large, single-grain YBCO bulk superconductors with good superconducting properties. 5 wt.% Ag doped Y211 green compacts were sintered at 900 .deg. C {approx} 1200 .deg.C and then a single crystal YBCO was fabricated by an infiltration method. A refinement and uniform distribution of the Y211 particles in the Y123 matrix were achieved by sintering the Ag-doped samples. This enhancement of the critical current density was ascribable to a fine dispersion of the Y211 particles, a low porosity and the presence of Ag particles. In addition, we have designed and manufactured large YBCO single domain with levitation force of 10-13 kg/cm{sup 2} using TSMG processing technique.

Energize Electrochemical Double Layer Capacitor by Introducing an Ambipolar Organic Redox Radical in Electrolyte.

Science.gov (United States)

Wang, Yonggang; Hu, Lintong; Zhang, Yue; Shi, Chao; Guo, Kai; Zhai, Tianyou; Li, Huiqiao

2018-05-24

Carbon based electrochemical double layer capacitors (EDLCs) generally exhibit high power and long life, but low energy density/capacitance. Pore/morphology optimization and pseudocapacitive materials modification of carbon materials have been used to improve electrode capacitance, but leading to the consumption of tap density, conductivity and stability. Introducing soluble redox mediators into electrolyte is a promising alternative to improve the capacitance of electrode. However, it is difficult to find one redox mediator that can provide additional capacitance for both positive and negative electrodes simultaneously. Here, an ambipolar organic radical, 2, 2, 6, 6-tetramethylpiperidinyloxyl (TEMPO) is first introduced to the electrolyte, which can substantially contribute additional pseudocapacitance by oxidation at the positive electrode and reduction at the negative electrode simultaneously. The EDLC with TEMPO mediator delivers an energy density as high as 51 Wh kg-1, 2.4 times of the capacitor without TEMPO, and a long cycle stability over 4000 cycles. The achieved results potentially point a new way to improve the energy density of EDLCs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of redox proteins using electrochemical methods

OpenAIRE

Verhagen, 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 information about the kinetics of electron transfer between proteins and about the dynamic behaviour of redox cofactors in proteins. This thesis describes the results of a study, initiated to get a ...

Test equipment for a flywheel energy storage system using a magnetic bearing composed of superconducting coils and superconducting bulks

International Nuclear Information System (INIS)

Ogata, M; Matsue, H; Yamashita, T; Hasegawa, H; Nagashima, K; Maeda, T; Matsuoka, T; Mukoyama, S; Shimizu, H; Horiuchi, S

2016-01-01

Energy storage systems are necessary for renewable energy sources such as solar power in order to stabilize their output power, which fluctuates widely depending on the weather. Since ‘flywheel energy storage systems’ (FWSSs) do not use chemical reactions, they do not deteriorate due to charge or discharge. This is an advantage of FWSSs in applications for renewable energy plants. A conventional FWSS has capacity limitation because of the mechanical bearings used to support the flywheel. Therefore, we have designed a superconducting magnetic bearing composed of a superconducting coil stator and a superconducting bulk rotor in order to solve this problem, and have experimentally manufactured a large scale FWSS with a capacity of 100 kWh and an output power of 300 kW. The superconducting magnetic bearing can levitate 4 tons and enables the flywheel to rotate smoothly. A performance confirmation test will be started soon. An overview of the superconducting FWSS is presented in this paper. (paper)

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals

Science.gov (United States)

Ambrosio, Francesco; Miceli, Giacomo; Pasquarello, Alfredo

2015-12-01

We investigate redox levels in aqueous solution using a combination of ab initio molecular dynamics (MD) simulations and thermodynamic integration methods. The molecular dynamics are performed with both the semilocal Perdew-Burke-Ernzerhof functional and a nonlocal functional (rVV10) accounting for van der Waals (vdW) interactions. The band edges are determined through three different schemes, namely, from the energy of the highest occupied and of the lowest unoccupied Kohn-Sham states, from total-energy differences, and from a linear extrapolation of the density of states. It is shown that the latter does not depend on the system size while the former two are subject to significant finite-size effects. For the redox levels, we provide a formulation in analogy to the definition of charge transition levels for defects in crystalline materials. We consider the H+/H2 level defining the standard hydrogen electrode, the OH-/OH∗ level corresponding to the oxidation of the hydroxyl ion, and the H2O/OH∗ level for the dehydrogenation of water. In spite of the large structural modifications induced in liquid water, vdW interactions do not lead to any significant structural effect on the calculated band gap and band edges. The effect on the redox levels is also small since the solvation properties of ionic species are little affected by vdW interactions. Since the electronic properties are not significantly affected by the underlying structural properties, it is justified to perform hybrid functional calculations on the configurations of our MD simulations. The redox levels calculated as a function of the fraction α of Fock exchange are found to remain constant, reproducing a general behavior previously observed for charge transition levels of defects. Comparison with experimental values shows very good agreement. At variance, the band edges and the band gap evolve linearly with α. For α ≃ 0.40, we achieve a band gap, band-edge positions, and redox levels in overall

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals

Energy Technology Data Exchange (ETDEWEB)

Ambrosio, Francesco, E-mail: Francesco.Ambrosio@epfl.ch; Miceli, Giacomo; Pasquarello, Alfredo [Chaire de Simulation à l’Echelle Atomique (CSEA), Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland)

2015-12-28

We investigate redox levels in aqueous solution using a combination of ab initio molecular dynamics (MD) simulations and thermodynamic integration methods. The molecular dynamics are performed with both the semilocal Perdew-Burke-Ernzerhof functional and a nonlocal functional (rVV10) accounting for van der Waals (vdW) interactions. The band edges are determined through three different schemes, namely, from the energy of the highest occupied and of the lowest unoccupied Kohn-Sham states, from total-energy differences, and from a linear extrapolation of the density of states. It is shown that the latter does not depend on the system size while the former two are subject to significant finite-size effects. For the redox levels, we provide a formulation in analogy to the definition of charge transition levels for defects in crystalline materials. We consider the H{sup +}/H{sub 2} level defining the standard hydrogen electrode, the OH{sup −}/OH{sup ∗} level corresponding to the oxidation of the hydroxyl ion, and the H{sub 2}O/OH{sup ∗} level for the dehydrogenation of water. In spite of the large structural modifications induced in liquid water, vdW interactions do not lead to any significant structural effect on the calculated band gap and band edges. The effect on the redox levels is also small since the solvation properties of ionic species are little affected by vdW interactions. Since the electronic properties are not significantly affected by the underlying structural properties, it is justified to perform hybrid functional calculations on the configurations of our MD simulations. The redox levels calculated as a function of the fraction α of Fock exchange are found to remain constant, reproducing a general behavior previously observed for charge transition levels of defects. Comparison with experimental values shows very good agreement. At variance, the band edges and the band gap evolve linearly with α. For α ≃ 0.40, we achieve a band gap, band

Dihydroxybenzene/benzoquinone-containing polymers: organic redox polymers

Energy Technology Data Exchange (ETDEWEB)

Moulay, S. [Universite de Blida, Lab. de Chimie-Physique Macromoleculaire, Institut de Chimie Industrielle (Algeria)

2000-08-01

Polymers containing hydroquinone, catechol or their corresponding benzoquinones are a special class of redox polymers. Three pathways of their syntheses are possible: condensation polymerization of suitable monomers, addition polymerization of vinyl monomers containing redox moiety, and chemical attachment of redox unit onto pre-made polymeric matrix. A range of functionalized matrices have been employed such as polyethers, polyesters, polycarbonates, polyurethanes, polyamides and others. Protection of their phenolic functionality has conducted to chemically interesting redox polymer precursors. The presence of a redox moiety coupled with the extant functionalization of the polymer matrix makes the materials very valuable, of wide properties and consequently of vast applicability. For instance, in the oil field, some polymers such as carboxy-methyl-cellulose (CMC) are often applied as to bring about a viscosity improvement and therefore to facilitate the oil drilling. In this regard, Patel evaluated sulfo-alkylated polymeric catechol, namely sulfo-methylated and sulfo-ethylated resins. Indeed, polymeric catechol chemically modified as such exhibited a marked ability to control the viscosity, the gel strength, as well as the filtrate loss of aqueous oil drilling fluids.

Renewable hydrogen generation from a dual-circuit redox flow battery

OpenAIRE

Amstutz, Veronique; Toghill, Kathryn Ellen; Powlesland, Francis; Vrubel, Heron; Comninellis, Christos; Hu, Xile; Girault, Hubert H.

2014-01-01

Redox flow batteries (RFBs) are particularly well suited for storing the intermittent excess supply of renewable electricity; so-called “junk” electricity. Conventional RFBs are charged and discharged electrochemically, with electricity stored as chemical energy in the electrolytes. In the RFB system reported here, the electrolytes are conventionally charged but are then chemically discharged over catalytic beds in separate external circuits. The catalytic reaction of particular interest gene...

Synthesis of bulk nanocrystalline Pb-Sn-Te alloy under high pressure

International Nuclear Information System (INIS)

Zhu, P W; Chen, L X; Jia, X; Ma, H A; Ren, G Z; Guo, W L; Liu, H J; Zou, G T

2002-01-01

Pb-Sn-Te bulk nanocrystalline (NC) materials are prepared successfully by quenching melts under high pressure. The mean particle size is about 100 nm and the crystal structure is NaCl type. The mechanism of formation of the bulk NC alloy is explained: there is an increasing of the nucleation rate and a decrease in the growth rate of nuclei with increase of pressure during the solidification processes. The thermoelectric properties of Pb-Sn-Te bulk NC alloy are enhanced. This method is promising for producing thermoelectric materials with improved high-energy conversion efficiency

Vascular remodeling: A redox-modulated mechanism of vessel caliber regulation.

Science.gov (United States)

Tanaka, Leonardo Y; Laurindo, Francisco R M

2017-08-01

Vascular remodeling, i.e. whole-vessel structural reshaping, determines lumen caliber in (patho)physiology. Here we review mechanisms underlying vessel remodeling, with emphasis in redox regulation. First, we discuss confusing terminology and focus on strictu sensu remodeling. Second, we propose a mechanobiological remodeling paradigm based on the concept of tensional homeostasis as a setpoint regulator. We first focus on shear-mediated models as prototypes of remodeling closely dominated by highly redox-sensitive endothelial function. More detailed discussions focus on mechanosensors, integrins, extracellular matrix, cytoskeleton and inflammatory pathways as potential of mechanisms potentially coupling tensional homeostasis to redox regulation. Further discussion of remodeling associated with atherosclerosis and injury repair highlights important aspects of redox vascular responses. While neointima formation has not shown consistent responsiveness to antioxidants, vessel remodeling has been more clearly responsive, indicating that despite the multilevel redox signaling pathways, there is a coordinated response of the whole vessel. Among mechanisms that may orchestrate redox pathways, we discuss roles of superoxide dismutase activity and extracellular protein disulfide isomerase. We then discuss redox modulation of aneurysms, a special case of expansive remodeling. We propose that the redox modulation of vascular remodeling may reflect (1) remodeling pathophysiology is dominated by a particularly redox-sensitive cell type, e.g., endothelial cells (2) redox pathways are temporospatially coordinated at an organ level across distinct cellular and acellular structures or (3) the tensional homeostasis setpoint is closely connected to redox signaling. The mechanobiological/redox model discussed here can be a basis for improved understanding of remodeling and helps clarifying mechanisms underlying prevalent hard-to-treat diseases. Copyright © 2017 Elsevier Inc. All

Redox-Based Regulation of Bacterial Development and Behavior.

Science.gov (United States)

Sporer, Abigail J; Kahl, Lisa J; Price-Whelan, Alexa; Dietrich, Lars E P

2017-06-20

Severe changes in the environmental redox potential, and resulting alterations in the oxidation states of intracellular metabolites and enzymes, have historically been considered negative stressors, requiring responses that are strictly defensive. However, recent work in diverse organisms has revealed that more subtle changes in the intracellular redox state can act as signals, eliciting responses with benefits beyond defense and detoxification. Changes in redox state have been shown to influence or trigger chromosome segregation, sporulation, aerotaxis, and social behaviors, including luminescence as well as biofilm establishment and dispersal. Connections between redox state and complex behavior allow bacteria to link developmental choices with metabolic state and coordinate appropriate responses. Promising future directions for this area of study include metabolomic analysis of species- and condition-dependent changes in metabolite oxidation states and elucidation of the mechanisms whereby the redox state influences circadian regulation.

Design of a Novel Voltage Controller for Conversion of Carbon Dioxide into Clean Fuels Using the Integration of a Vanadium Redox Battery with Solar Energy

Directory of Open Access Journals (Sweden)

Ting-Chia Ou

2018-02-01

Full Text Available This letter presents a design for a novel voltage controller (NVC which can exhibit three different reactions using the integration of a vanadium redox battery (VRB with solar energy, and uses only electrochemical potentials with optimal external bias voltage control to carry out hydrogen production and the conversion of carbon dioxide (CO2 into methane and methanol. This NVC is simply constructed by using dynamic switch and control strategies with a time-variant control system. In this design, the interval voltage bias solutions obtained by the proposed NVC exhibit better voltage ranges and good agreement with the practical scenarios, which will bring significant benefits to operation for continuous reduction of CO2 into value-added clean fuels using the integration of a VRB with solar energy or any other renewable energy resource for future applications.

Copper nanoparticle-deposited graphite felt electrodes for all vanadium redox flow batteries

International Nuclear Information System (INIS)

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

2016-01-01

Highlights: • Copper nanoparticle is proposed as electrocatalyst for VRFBs for the first time. • Propose a binder-free copper nanoparticle decorated electrode. • The energy efficiency is up to 80.1% at 300 mA cm"−"2, enhancing more than 17%. • High stability and capacity retention are achieved by battery with copper catalyst. - Abstract: A copper nanoparticle deposited graphite felt electrode for all vanadium redox flow batteries (VRFBs) is developed and tested. It is found that the copper catalyst enables a significant improvement in the electrochemical kinetics of the V"3"+/V"2"+ redox reaction. The battery’s utilization of the electrolyte and energy efficiency are found to be as high as 83.7% and 80.1%, at a current density of 300 mA cm"−"2, which are 53.1% and 17.8% higher than those of the battery without the catalyst. Moreover, the present battery shows a good stability during the cycle test. The results suggest that the inexpensive copper nanoparticle catalyst without tedious preparation process offers a great promise for VRFB application.

Effect of redox conditions on pharmaceutical loss during biological wastewater treatment using sequencing batch reactors

Energy Technology Data Exchange (ETDEWEB)

Stadler, Lauren B., E-mail: lstadler@umich.edu [Department of Civil and Environmental Engineering, University of Michigan, 1351 Beal Avenue, EWRE, Ann Arbor, MI 48109 (United States); Su, Lijuan, E-mail: lijuansu@buffalo.edu [Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260 (United States); Moline, Christopher J., E-mail: christopher.moline@hdrinc.com [Department of Civil and Environmental Engineering, University of Michigan, 1351 Beal Avenue, EWRE, Ann Arbor, MI 48109 (United States); Ernstoff, Alexi S., E-mail: alexer@dtu.dk [Department of Civil and Environmental Engineering, University of Michigan, 1351 Beal Avenue, EWRE, Ann Arbor, MI 48109 (United States); Aga, Diana S., E-mail: dianaaga@buffalo.edu [Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260 (United States); Love, Nancy G., E-mail: nglove@umich.edu [Department of Civil and Environmental Engineering, University of Michigan, 1351 Beal Avenue, EWRE, Ann Arbor, MI 48109 (United States)

2015-01-23

Highlights: • Pharmaceutical fate was studied in SBRs operated at different redox conditions. • Stable carbon oxidation and nitrification occurred under microaerobic conditions. • Losses of atenolol and trimethoprim were highest under fully aerobic conditions. • Loss of sulfamethoxazole was highest under microaerobic conditions. • Deconjugation occurred during treatment to form sulfamethoxazole and desvenlafaxine. - Abstract: We lack a clear understanding of how wastewater treatment plant (WWTP) process parameters, such as redox environment, impact pharmaceutical fate. WWTPs increasingly install more advanced aeration control systems to save energy and achieve better nutrient removal performance. The impact of redox condition, and specifically the use of microaerobic (low dissolved oxygen) treatment, is poorly understood. In this study, the fate of a mixture of pharmaceuticals and several of their transformation products present in the primary effluent of a local WWTP was assessed in sequencing batch reactors operated under different redox conditions: fully aerobic, anoxic/aerobic, and microaerobic (DO concentration ≈0.3 mg/L). Among the pharmaceuticals that were tracked during this study (atenolol, trimethoprim, sulfamethoxazole, desvenlafaxine, venlafaxine, and phenytoin), overall loss varied between them and between redox environments. Losses of atenolol and trimethoprim were highest in the aerobic reactor; sulfamethoxazole loss was highest in the microaerobic reactors; and phenytoin was recalcitrant in all reactors. Transformation products of sulfamethoxazole and desvenlafaxine resulted in the reformation of their parent compounds during treatment. The results suggest that transformation products must be accounted for when assessing removal efficiencies and that redox environment influences the degree of pharmaceutical loss.

Effect of redox conditions on pharmaceutical loss during biological wastewater treatment using sequencing batch reactors

International Nuclear Information System (INIS)

Stadler, Lauren B.; Su, Lijuan; Moline, Christopher J.; Ernstoff, Alexi S.; Aga, Diana S.; Love, Nancy G.

2015-01-01

Highlights: • Pharmaceutical fate was studied in SBRs operated at different redox conditions. • Stable carbon oxidation and nitrification occurred under microaerobic conditions. • Losses of atenolol and trimethoprim were highest under fully aerobic conditions. • Loss of sulfamethoxazole was highest under microaerobic conditions. • Deconjugation occurred during treatment to form sulfamethoxazole and desvenlafaxine. - Abstract: We lack a clear understanding of how wastewater treatment plant (WWTP) process parameters, such as redox environment, impact pharmaceutical fate. WWTPs increasingly install more advanced aeration control systems to save energy and achieve better nutrient removal performance. The impact of redox condition, and specifically the use of microaerobic (low dissolved oxygen) treatment, is poorly understood. In this study, the fate of a mixture of pharmaceuticals and several of their transformation products present in the primary effluent of a local WWTP was assessed in sequencing batch reactors operated under different redox conditions: fully aerobic, anoxic/aerobic, and microaerobic (DO concentration ≈0.3 mg/L). Among the pharmaceuticals that were tracked during this study (atenolol, trimethoprim, sulfamethoxazole, desvenlafaxine, venlafaxine, and phenytoin), overall loss varied between them and between redox environments. Losses of atenolol and trimethoprim were highest in the aerobic reactor; sulfamethoxazole loss was highest in the microaerobic reactors; and phenytoin was recalcitrant in all reactors. Transformation products of sulfamethoxazole and desvenlafaxine resulted in the reformation of their parent compounds during treatment. The results suggest that transformation products must be accounted for when assessing removal efficiencies and that redox environment influences the degree of pharmaceutical loss

Redox Cycling Realized in Paper-Based Biochemical Sensor for Selective Detection of Reversible Redox Molecules Without Micro/Nano Fabrication Process.

Science.gov (United States)

Yamamoto, So; Uno, Shigeyasu

2018-02-28

This paper describes a paper-based biochemical sensor that realizes redox cycling with close interelectrode distance. Two electrodes, the generator and collector electrodes, can detect steady-state oxidation and reduction currents when suitable potential is held at each electrode. The sensor has two gold plates on both sides of a piece of chromatography paper and defines the interelectrode distance by the thickness of the paper (180 μm) without any micro-fabrication processes. Our proposed sensor geometry has successfully exhibited signatures of redox cycling. As a result, the concentration of ferrocyanide as reversible redox molecules was successfully quantified under the interference by ascorbic acid as a strong irreversible reducing agent. This was possible because the ascorbic acids are completely consumed by the irreversible reaction, while maintaining redox cycling of reversible ferrocyanide. This suggests that a sensor based on the redox cycling method will be suitable for detecting target molecules at low concentration.