Showing papers on "Redox published in 2011"

Porphyrin-Sensitized Solar Cells with Cobalt (II/III)–Based Redox Electrolyte Exceed 12 Percent Efficiency

Abstract: The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co(II/III)tris(bipyridyl)–based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.

Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency (vol 334, pg 629, 2011)

Abstract: Simultaneous modification of the dye and redox shuttle boosts the efficiency of a dye-sensitized solar cell. The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co(II/III)tris(bipyridyl)–based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.

Copper-Catalyzed Aerobic Oxidative C ? H Functionalizations: Trends and Mechanistic Insights

Abstract: The selective oxidation of C-H bonds and the use of O(2) as a stoichiometric oxidant represent two prominent challenges in organic chemistry. Copper(II) is a versatile oxidant, capable of promoting a wide range of oxidative coupling reactions initiated by single-electron transfer (SET) from electron-rich organic molecules. Many of these reactions can be rendered catalytic in Cu by employing molecular oxygen as a stoichiometric oxidant to regenerate the active copper(II) catalyst. Meanwhile, numerous other recently reported Cu-catalyzed C-H oxidation reactions feature substrates that are electron-deficient or appear unlikely to undergo single-electron transfer to copper(II). In some of these cases, evidence has been obtained for the involvement of organocopper(III) intermediates in the reaction mechanism. Organometallic C-H oxidation reactions of this type represent important new opportunities for the field of Cu-catalyzed aerobic oxidations.

Water-oxidation catalysis by manganese in a geochemical-like cycle

Abstract: Water oxidation in all oxygenic photosynthetic organisms is catalysed by the Mn₄CaO₄ cluster of Photosystem II. This cluster has inspired the development of synthetic manganese catalysts for solar energy production. A photoelectrochemical device, made by impregnating a synthetic tetranuclear-manganese cluster into a Nafion matrix, has been shown to achieve efficient water oxidation catalysis. We report here in situ X-ray absorption spectroscopy and transmission electron microscopy studies that demonstrate that this cluster dissociates into Mn(II) compounds in the Nafion, which are then reoxidized to form dispersed nanoparticles of a disordered Mn(III/IV)-oxide phase. Cycling between the photoreduced product and this mineral-like solid is responsible for the observed photochemical water-oxidation catalysis. The original manganese cluster serves only as a precursor to the catalytically active material. The behaviour of Mn in Nafion therefore parallels its broader biogeochemistry, which is also dominated by cycles of oxidation into solid Mn(III/IV) oxides followed by photoreduction to Mn²⁺.

Anticancer activity of metal complexes: involvement of redox processes.

Abstract: Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with t...

A Cobalt–Dithiolene Complex for the Photocatalytic and Electrocatalytic Reduction of Protons

Abstract: The complex [Co(bdt)2]− (where bdt = 1,2-benzenedithiolate) is an active catalyst for the visible light driven reduction of protons from water when employed with Ru(bpy)32+ as the photosensitizer and ascorbic acid as the sacrificial electron donor. At pH 4.0, the system exhibits very high activity, achieving >2700 turnovers with respect to catalyst and an initial turnover rate of 880 mol H2/mol catalyst/h. The same complex is also an active electrocatalyst for proton reduction in 1:1 CH3CN/H2O in the presence of weak acids, with the onset of a catalytic wave at the reversible redox couple of −1.01 V vs Fc+/Fc. The cobalt–dithiolene complex [Co(bdt)2]− thus represents a highly active catalyst for both the electrocatalytic and photocatalytic reduction of protons in aqueous solutions.

Towards electrosynthesis in shewanella: energetics of reversing the mtr pathway for reductive metabolism.

Abstract: Bioelectrochemical systems rely on microorganisms to link complex oxidation/reduction reactions to electrodes. For example, in Shewanella oneidensis strain MR-1, an electron transfer conduit consisting of cytochromes and structural proteins, known as the Mtr respiratory pathway, catalyzes electron flow from cytoplasmic oxidative reactions to electrodes. Reversing this electron flow to drive microbial reductive metabolism offers a possible route for electrosynthesis of high value fuels and chemicals. We examined electron flow from electrodes into Shewanella to determine the feasibility of this process, the molecular components of reductive electron flow, and what driving forces were required. Addition of fumarate to a film of S. oneidensis adhering to a graphite electrode poised at −0.36 V versus standard hydrogen electrode (SHE) immediately led to electron uptake, while a mutant lacking the periplasmic fumarate reductase FccA was unable to utilize electrodes for fumarate reduction. Deletion of the gene encoding the outer membrane cytochrome-anchoring protein MtrB eliminated 88% of fumarate reduction. A mutant lacking the periplasmic cytochrome MtrA demonstrated more severe defects. Surprisingly, disruption of menC, which prevents menaquinone biosynthesis, eliminated 85% of electron flux. Deletion of the gene encoding the quinone-linked cytochrome CymA had a similar negative effect, which showed that electrons primarily flowed from outer membrane cytochromes into the quinone pool, and back to periplasmic FccA. Soluble redox mediators only partially restored electron transfer in mutants, suggesting that soluble shuttles could not replace periplasmic protein-protein interactions. This work demonstrates that the Mtr pathway can power reductive reactions, shows this conduit is functionally reversible, and provides new evidence for distinct CymA:MtrA and CymA:FccA respiratory units.

Biochemistry, evolution and physiological function of the Rnf complex, a novel ion-motive electron transport complex in prokaryotes

Abstract: Microbes have a fascinating repertoire of bioenergetic enzymes and a huge variety of electron transport chains to cope with very different environmental conditions, such as different oxygen concentrations, different electron acceptors, pH and salinity. However, all these electron transport chains cover the redox span from NADH + H(+) as the most negative donor to oxygen/H(2)O as the most positive acceptor or increments thereof. The redox range more negative than -320 mV has been largely ignored. Here, we have summarized the recent data that unraveled a novel ion-motive electron transport chain, the Rnf complex, that energetically couples the cellular ferredoxin to the pyridine nucleotide pool. The energetics of the complex and its biochemistry, as well as its evolution and cellular function in different microbes, is discussed.

Understanding the Role of the Sulfide Redox Couple (S2–/Sn2–) in Quantum Dot-Sensitized Solar Cells

Abstract: The presence of sulfide/polysulfide redox couple is crucial in achieving stability of metal chalcogenide (e.g., CdS and CdSe)-based quantum dot-sensitized solar cells (QDSC). However, the interfacial charge transfer processes play a pivotal role in dictating the net photoconversion efficiency. We present here kinetics of hole transfer, characterization of the intermediates involved in the hole oxidation of sulfide ion, and the back electron transfer between sulfide radical and electrons injected into TiO2 nanoparticles. The kinetic rate constant (107–109 s–1) for the hole transfer obtained from the emission lifetime measurements suggests slow hole scavenging from CdSe by S2– is one of the limiting factors in attaining high overall efficiency. The presence of the oxidized couple, by addition of S or Se to the electrolyte, increases the photocurrent, but it also enhances the rate of back electron transfer.

Superoxide Dismutase in Redox Biology: The roles of superoxide and hydrogen peroxide

Abstract: Superoxide dismutases (SOD) are considered to be antioxidant enzymes. This view came about because its substrate, superoxide, is a free radical; in the era of their discovery, 1960’s – 1970’s, the general mindset was that free radicals in biology must be damaging. Indeed SOD blunts the cascade of oxidations initiated by superoxide. However in the late 1970’s it was observed that cancer cells that have low activity of the mitochondrial form of SOD, MnSOD, grow faster than those with higher activities of MnSOD. These observations indicated that SOD, superoxide, and hydrogen peroxide affected the basic biology of cells and tissues, not just via damaging oxidation reactions. It is now realized that superoxide and hydrogen peroxide are essential for normal cellular and organism function. MnSOD appears to be a central player in the redox biology of cells and tissues.

Noble metal-free hydrazine fuel cell catalysts: EPOC effect in competing chemical and electrochemical reaction pathways.

Abstract: We report the discovery of a highly active Ni−Co alloy electrocatalyst for the oxidation of hydrazine (N2H4) and provide evidence for competing electrochemical (faradaic) and chemical (nonfaradaic) reaction pathways. The electrochemical conversion of hydrazine on catalytic surfaces in fuel cells is of great scientific and technological interest, because it offers multiple redox states, complex reaction pathways, and significantly more favorable energy and power densities compared to hydrogen fuel. Structure−reactivity relations of a Ni60Co40 alloy electrocatalyst are presented with a 6-fold increase in catalytic N2H4 oxidation activity over today’s benchmark catalysts. We further study the mechanistic pathways of the catalytic N2H4 conversion as function of the applied electrode potential using differentially pumped electrochemical mass spectrometry (DEMS). At positive overpotentials, N2H4 is electrooxidized into nitrogen consuming hydroxide ions, which is the fuel cell-relevant faradaic reaction pathway....

Mechanisms of Energy Storage in Carbon-Based Supercapacitors Modified with a Quinoid Redox-Active Electrolyte

Abstract: The mechanisms involved in the storage of energy in carbon-based supercapacitors modified by the addition of an electrochemically active compound (quinone/hydroquinone, Q/HQ) into the electrolyte (H2SO4) are investigated. Besides the charging of the double-layer characteristic of carbon materials, galvanostatic cycling experiments performed on each electrode revealed a battery-type behavior in the anode and a pseudocapacitive hydrogen electrosorption process in the cathode as a consequence of an asymmetric split of voltage between the electrodes after the incorporation of HQ. Both the hydrogen electrosorption and Q/HQ redox reactions were studied in depth from the cyclic voltammograms obtained for both electrolytes in a three-electrode cell. An outstanding specific capacitance value of 5017 F g–1 was attained by the anode due to the development of the quinoid redox reactions on its surface. Meanwhile, the cathode capacitance also increased significantly with respect to the value obtained by the supercapac...

Organic Radical Battery Approaching Practical Use

Abstract: The electrochemical redox reactions of organic polymers bearing robust unpaired electrons were investigated to determine the applicability of these polymers to rechargeable batteries. Such an “orga...

Polarization curve analysis of all-vanadium redox flow batteries

Abstract: We outline the analysis of performance of redox flow batteries (RFBs) using polarization curves. This method allows the researcher immediate access to sources of performance losses in flow batteries operating at steady state. We provide guidance on ‘best practices’ for use of this tool, illustrated using examples from single cells operating as vanadium redox batteries.

Electrochemical Analysis of Proton and Electron Transfer Equilibria of the Reducible Moieties in Humic Acids

Abstract: Humic substances play a key role in biogeochemical and pollutant redox reactions. The objective of this work was to characterize the proton and electron transfer equilibria of the reducible moieties in different humic acids (HA). Cyclic voltammetry experiments demonstrated that diquat and ethylviologen mediated electron transfer between carbon working electrodes and HA. These compounds were used also to facilitate attainment of redox equilibria between redox electrodes and HA in potentiometric Eh measurements. Bulk electrolysis of HA combined with pH-stat acid titration demonstrated that electron transfer to the reducible moieties in HA also resulted in proton uptake, suggesting decreasing reduction potentials Eh of HA with increasing pH. This was confirmed by potentiometric Eh-pH titrations of HA at different redox states. Eh measurements of HA samples prereduced to different redox states by bulk electrolysis revealed reducible moieties in HA that cover a wide range of apparent standard reduction potenti...

Catalytic mechanism of water oxidation with single-site ruthenium-heteropolytungstate complexes.

Abstract: Catalytic water oxidation to generate oxygen was achieved using all-inorganic mononuclear ruthenium complexes bearing Keggin-type lacunary heteropolytungstate, [RuIII(H2O)SiW11O39]5– (1) and [RuIII(H2O)GeW11O39]5– (2), as catalysts with (NH4)2[CeIV(NO3)6] (CAN) as a one-electron oxidant in water. The oxygen atoms of evolved oxygen come from water as confirmed by isotope-labeled experiments. Cyclic voltammetric measurements of 1 and 2 at various pH’s indicate that both complexes 1 and 2 exhibit three one-electron redox couples based on ruthenium center. The Pourbaix diagrams (plots of E1/2 vs pH) support that the Ru(III) complexes are oxidized to the Ru(V)–oxo complexes with CAN. The Ru(V)–oxo complex derived from 1 was detected by UV–visible absorption, EPR, and resonance Raman measurements in situ as an active species during the water oxidation reaction. This indicates that the Ru(V)–oxo complex is involved in the rate-determining step of the catalytic cycle of water oxidation. The overall catalytic mech...

Novel regulators in photosynthetic redox control of plant metabolism and gene expression.

Abstract: Reduction-oxidation (redox) reactions are an essential part of cell metabolism and represent a major fraction of all catabolic and anabolic reactions. Their dominant characteristic is that they generate and consume compounds with in part highly negative redox potential. Redox reactions occur at many