scholarly journals Electrolyte Composition in Li/O2 Batteries with LiI Redox Mediators: Solvation Effects on Redox Potentials and Implications for Redox Shuttling

2018 ◽  
Vol 122 (3) ◽  
pp. 1522-1534 ◽  
Author(s):  
Azusa Nakanishi ◽  
Morgan L. Thomas ◽  
Hoi-Min Kwon ◽  
Yuki Kobayashi ◽  
Ryoichi Tatara ◽  
...  
Keyword(s):  
Electrolyte Composition ◽  
Redox Potentials ◽  
Redox Mediators ◽  
Solvation Effects

scholarly journals Laccases: Versatile Biocatalysts for the Synthesis of Heterocyclic Cores

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3719
Author(s):  
Ana Catarina Sousa ◽  
Lígia O. Martins ◽  
M. Paula Robalo
Keyword(s):  
Membered Ring ◽  
Low Molecular Weight ◽  
Redox Potentials ◽  
Redox Mediators ◽  
Multicopper Oxidases ◽  
Phenothiazine Derivatives ◽  
Ph Values ◽  
Electron Shuttles ◽  
Specific Oxidation ◽  
Optimal Ph

Laccases are multicopper oxidases that have shown a great potential in various biotechnological and green chemistry processes mainly due to their high relative non-specific oxidation of phenols, arylamines and some inorganic metals, and their high redox potentials that can span from 500 to 800 mV vs. SHE. Other advantages of laccases include the use of readily available oxygen as a second substrate, the formation of water as a side-product and no requirement for cofactors. Importantly, addition of low-molecular-weight redox mediators that act as electron shuttles, promoting the oxidation of complex bulky substrates and/or of higher redox potential than the enzymes themselves, can further expand their substrate scope, in the so-called laccase-mediated systems (LMS). Laccase bioprocesses can be designed for efficiency at both acidic and basic conditions since it is known that fungal and bacterial laccases exhibit distinct optimal pH values for the similar phenolic and aromatic amines. This review covers studies on the synthesis of five- and six-membered ring heterocyclic cores, such as benzimidazoles, benzofurans, benzothiazoles, quinazoline and quinazolinone, phenazine, phenoxazine, phenoxazinone and phenothiazine derivatives. The enzymes used and the reaction protocols are briefly outlined, and the mechanistic pathways described.

scholarly journals Sharp kinetic acceleration potentials during mediated redox catalysis of insulators

2021 ◽  
Author(s):  
Deqing Cao ◽  
Xiaoxiao Shen ◽  
Aiping Wang ◽  
Fengjiao Yu ◽  
Yuping Wu ◽  
...  
Keyword(s):  
Redox Potentials ◽  
Redox Catalysis ◽  
Redox Mediators ◽  
Fast Kinetics ◽  
Surface Conditions ◽  
Storage Materials ◽  
Surface Facets

Abstract Redox mediators could catalyse otherwise slow and energy-inefficient cycling of Li-S and Li-O2 batteries by shuttling electrons/holes between the electrode and the solid insulating storage materials. For mediators to work efficiently they need to oxidize the solid with fast kinetics yet the lowest possible overpotential. Here, we found that when the redox potentials of mediators are tuned via, e.g., Li+ concentration in the electrolyte, they exhibit distinct threshold potentials, where the kinetics accelerate several-fold within a range as small as 10 mV. This phenomenon is independent of types of mediators and electrolyte. The acceleration originates from the overpotentials required to activate fast Li+/e– extraction and the following chemical step at specific abundant surface facets. Efficient redox catalysis at insulating solids requires therefore carefully considering the surface conditions of the storage materials and electrolyte-dependent redox potentials, which may be tuned by salt concentrations or solvents.

Catalytic effects of different redox mediators on the reductive decolorization of azo dyes

2006 ◽  
Vol 54 (2) ◽  
pp. 165-170 ◽  
Author(s):  
A.A. Encinas-Yocupicio ◽  
E. Razo-Flores ◽  
F. Sánchez-Díaz ◽  
A.B. dos Santos ◽  
J.A. Field ◽  
...  
Keyword(s):  
Azo Dyes ◽  
Granular Sludge ◽  
Order Rate Constant ◽  
Anaerobic Treatment ◽  
Redox Mediator ◽  
Redox Potentials ◽  
Redox Mediators ◽  
Direct Blue ◽  
Reactive Orange ◽  
Catalytic Effects

The catalytic effects of redox mediators, with distinct standard redox potentials (E′0), were evaluated on the first-order rate constant of decolorization (Kd) of recalcitrant azo dyes by an anaerobic granular sludge. The dyes studied included mono-azo (Reactive Orange 14, RO14), di-azo (Direct Blue 53, DB53), and tri-azo (Direct Blue 71, DB71) compounds. Toxicity and auto-catalytic aspects seemed to play a role in determining the rate of decolorization. Addition of riboflavin, anthraquinone-2,6-disulphonate (AQDS) or lawsone as a redox mediator, increased the Kd value for all dyes studied, although their impact varied in every case. Kd values were increased from 1.1-fold up to 3.8-fold depending on the redox mediator applied. Moreover, catalysts with moderately similar E′0 value caused distinct stimulation on the rate of decolorization. These results should be considered for selecting the proper redox mediator to be applied during the anaerobic treatment of textile wastewaters and effluents containing electron-withdrawing pollutants, such as nitro-aromatic and polychlorinated compounds.

Density functional calculations of redox potentials for FeS clusters including solvation effects

1993 ◽  
Vol 51 (1-2) ◽  
pp. 449 ◽  
Author(s):  
Jun Liang Chen ◽  
Jean-Marie Mouesca ◽  
Louis Noodleman ◽  
David A. Case ◽  
Donald Bashford
Keyword(s):  
Density Functional Calculations ◽  
Density Functional ◽  
Redox Potentials ◽  
Solvation Effects

Investigation of cobalt redox mediators and effects of TiO2 film topology in dye-sensitized solar cells

RSC Advances ◽  
2016 ◽  
Vol 6 (61) ◽  
pp. 56580-56588 ◽  
Author(s):  
Majid Safdari ◽  
Peter W. Lohse ◽  
Leif Häggman ◽  
Sara Frykstrand ◽  
Daniel Högberg ◽  
...  
Keyword(s):  
Solar Cells ◽  
Light Absorption ◽  
Dye Sensitized Solar Cells ◽  
Cobalt Complexes ◽  
Redox Potentials ◽  
Redox Mediators ◽  
Visible Light Absorption ◽  
Dye Sensitized ◽  
Sensitized Solar Cells ◽  
Interesting Alternative

Cobalt complexes represent interesting alternative redox mediators in dye-sensitized solar cells, with weak visible light absorption and a wide variety in redox potentials. Its diffusion in mesoporous TiO2 may, however, limit its performance.

Electrolytic Isolation of Twin-Type Shock Deformation Structures

1967 ◽  
Vol 25 ◽  
pp. 318-319
Author(s):  
F. I. Grace ◽  
L. E. Murr
Keyword(s):  
Grain Boundaries ◽  
Thin Foil ◽  
Electrolyte Composition ◽  
Experimental Conditions ◽  
Average Current Density ◽  
Electron Transmission ◽  
Deformation Structures ◽  
The Matrix ◽  
Average Current ◽  
Specimen Edge

During the course of electron transmission investigations of the deformation structures associated with shock-loaded thin foil specimens of 70/30 brass, it was observed that in a number of instances preferential etching occurred along grain boundaries; and that the degree of etching appeared to depend upon the various experimental conditions prevailing during electropolishing. These included the electrolyte composition, the average current density, and the temperature in the vicinity of the specimen. In the specific case of 70/30 brass shock-loaded at pressures in the range 200-400 kilobars, the predominant mode of deformation was observed to be twin-type faults which in several cases exhibited preferential etching similar to that observed along grain boundaries. A novel feature of this particular phenomenon was that in certain cases, especially for twins located in the vicinity of the specimen edge, the etching or preferential electropolishing literally isolated these structures from the matrix.

Using A Segmented Voltage Sweep Mode and A Gaussian Curve Fitting Method to Improve Heavy Metal Measurement System Performance

2012 ◽  
Vol 19 (2) ◽  
pp. 381-394
Author(s):  
José Pereira ◽  
Octavian Postolache ◽  
Pedro Girão
Keyword(s):  
Heavy Metals ◽  
Heavy Metal ◽  
Measurement System ◽  
Curve Fitting ◽  
System Performance ◽  
Redox Potentials ◽  
Voltage Sweep ◽  
Gaussian Curve ◽  
Fitting Method ◽  
Curve Fitting Method

Using A Segmented Voltage Sweep Mode and A Gaussian Curve Fitting Method to Improve Heavy Metal Measurement System PerformanceThis paper presents a voltammetric segmented voltage sweep mode that can be used to identify and measure heavy metals' concentrations. The proposed sweep mode covers a set of voltage ranges that are centered around the redox potentials of the metals that are under analysis. The heavy metal measurement system can take advantage of the historical database of measurements to identify the metals with higher concentrations in a given geographical area, and perform a segmented sweep around predefined voltage ranges or, alternatively, the system can perform a fast linear voltage sweep to identify the voltammetric current peaks and then perform a segmented voltage sweep around the set of voltages that are associated with the voltammetric current peaks. The paper also includes the presentation of two auto-calibration modes that can be used to improve system's reliability and proposes the usage of a Gaussian curve fitting of voltammetric data to identify heavy metals and to evaluate their concentrations. Several simulation and experimental results, that validate the theoretical expectations, are also presented in the paper.

An NADH-Inspired Redox Mediator Strategy to Promote Second-Sphere Electron and Proton Transfer for Cooperative Electrochemical CO2 Reduction Catalyzed by Iron Porphyrin

2020 ◽  
Author(s):  
Peter T. Smith ◽  
Sophia Weng ◽  
Christopher Chang
Keyword(s):  
Proton Transfer ◽  
Co2 Reduction ◽  
Iron Porphyrin ◽  
Redox Mediators ◽  
Reservoir Properties ◽  
Proton Reduction ◽  
Electrochemical Co2 Reduction ◽  
Starting Point ◽  
Rate Improvement ◽  
Molecular Catalysts

We present a bioinspired strategy for enhancing electrochemical carbon dioxide reduction catalysis by cooperative use of base-metal molecular catalysts with intermolecular second-sphere redox mediators that facilitate both electron and proton transfer. Functional synthetic mimics of the biological redox cofactor NADH, which are electrochemically stable and are capable of mediating both electron and proton transfer, can enhance the activity of an iron porphyrin catalyst for electrochemical reduction of CO<sub>2</sub> to CO, achieving a 13-fold rate improvement without altering the intrinsic high selectivity of this catalyst platform for CO<sub>2</sub> versus proton reduction. Evaluation of a systematic series of NADH analogs and redox-inactive control additives with varying proton and electron reservoir properties reveals that both electron and proton transfer contribute to the observed catalytic enhancements. This work establishes that second-sphere dual control of electron and proton inventories is a viable design strategy for developing more effective electrocatalysts for CO<sub>2</sub> reduction, providing a starting point for broader applications of this approach to other multi-electron, multi-proton transformations.

1,1’-Biaceanthrylene and 2,2'-Biaceanthrylene: Models for Linking Larger Polycyclic Aromatic Hydrocarbons via Five-Membered Rings

2019 ◽  
Author(s):  
Yachu Du ◽  
Kyle Plunkett
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Polycyclic Aromatic Hydrocarbon ◽  
Aromatic Hydrocarbon ◽  
Electronic Properties ◽  
Aromatic Hydrocarbons ◽  
Model Systems ◽  
Redox Potentials ◽  
Dimer Model ◽  
Optical And Electronic Properties ◽  
Polycyclic Aromatic

We show that polycyclic aromatic hydrocarbon (PAH) chromophores that are linked between two five-membered rings can access planarized structures with reduced optical gaps and redox potentials. Two aceanthrylene chromophores were connected into dimer model systems with the chromophores either projected outward (2,2’-biaceanthrylene) or inward (1,1’-biaceanthrylene) and the optical and electronic properties were compared. Only the planar 2,2’-biaceanthrylene system showed significant reductions of the optical gaps (1 eV) and redox potentials in relation to the aceanthrylene monomer.<br>

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