Electron-Transfer Studies of Model Redox-Active Species (Cationic, Anionic, and Neutral) in Deep Eutectic Solvents

2018 ◽  
Vol 122 (44) ◽  
pp. 25411-25421 ◽  
Author(s):  
Anu Renjith ◽  
V. Lakshminarayanan
Keyword(s):  
Electron Transfer ◽  
Deep Eutectic Solvents ◽  
Active Species ◽  
Redox Active

Ammonium tetrathiomolybdate as a novel electrode material for convenient tuning of the kinetics of electrochemical O2 reduction by using iron–porphyrin catalysts

2016 ◽  
Vol 4 (18) ◽  
pp. 6819-6823 ◽  
Author(s):  
Sudipta Chatterjee ◽  
Kushal Sengupta ◽  
Sabyasachi Bandyopadhyay ◽  
Abhishek Dey
Keyword(s):  
Electron Transfer ◽  
Electrode Material ◽  
Deposition Time ◽  
Active Species ◽  
Iron Porphyrin ◽  
Gold Electrodes ◽  
Redox Active ◽  
O2 Reduction ◽  
Ammonium Tetrathiomolybdate ◽  
Kinetics Of

Ammonium tetrathiomolybdate modified gold electrodes can easily tune the rate of electron transfer to the redox active species when the deposition time is varied.

scholarly journals How to Control the Rate of Heterogeneous Electron Transfer Across the Rim of M6L12 and M12L24 Nanospheres

2020 ◽  
Author(s):  
Riccardo Zaffaroni ◽  
Eduard.O. Bobylev ◽  
Plessius, Raoul ◽  
Jarl Ivar van der Vlugt ◽  
Joost reek
Keyword(s):  
Electron Transfer ◽  
Active Species ◽  
Transition Metal Catalysts ◽  
Supramolecular Assemblies ◽  
Fine Tuning ◽  
Transfer Rates ◽  
Heterogeneous Electron Transfer ◽  
Redox Active ◽  
Kinetics Of ◽  
Fine Tune

Catalysis in confined spaces, such as provided by supramolecular cages, is quickly gaining momentum. It allows for second coordination sphere strategies to control the selectivity and activity of transition metal catalysts, beyond the classical methods like fine-tuning the steric and electronic properties of the coordinating ligands. Only a few electrocatalytic reactions within cages have been reported, and there is no information regarding the electron transfer kinetics and thermodynamics of redox-active species encapsulated into supramolecular assemblies. This contribution revolves around the preparation of M<sub>6</sub>L<sub>12 </sub>and larger M<sub>12</sub>L<sub>24</sub> (M= Pd or Pt) nanospheres functionalized with different numbers of redox-active probes encapsulated within their cavity, either in a covalent fashion via different types of linkers (flexible, rigid and conjugated or rigid and non-conjugated) or by supramolecular hydrogen bonding interactions. The redox-probes can be addressed by electrochemical electron transfer across the rim of nanospheres and the thermodynamics and kinetics of this process are described. Our study identifies that the linker type and the number of redox probes within the cage are useful handles to fine-tune the electron transfer rates, paving the way for the encapsulation of electro-active catalysts and electrocatalytic applications of such supramolecular assemblies.

scholarly journals Electrical conductivity in two mixed-valence liquids

2015 ◽  
Vol 17 (21) ◽  
pp. 14107-14114 ◽  
Author(s):  
Wenzhi Yao ◽  
Steven P. Kelley ◽  
Robin D. Rogers ◽  
Thomas P. Vaid
Keyword(s):  
Electrical Conductivity ◽  
Electron Transfer ◽  
Exchange Rate ◽  
Rate Constants ◽  
Room Temperature ◽  
Mixed Valence ◽  
Electrical Current ◽  
Active Species ◽  
Redox Active

Two mixed-valence room-temperature liquids are reported: BuFc–[BuFc+][NTf2−] (BuFc = n-butylferrocene) and TEMPO–[TEMPO+][NTf2−]. Both are conductors of DC electrical current, and their conductivity is modeled based on the electron-transfer self-exchange rate constants of their constituent redox-active species.

scholarly journals How to Control the Rate of Heterogeneous Electron Transfer Across the Rim of M6L12 and M12L24 Nanospheres

2020 ◽  
Author(s):  
Riccardo Zaffaroni ◽  
Eduard.O. Bobylev ◽  
Plessius, Raoul ◽  
Jarl Ivar van der Vlugt ◽  
Joost reek
Keyword(s):  
Electron Transfer ◽  
Active Species ◽  
Transition Metal Catalysts ◽  
Supramolecular Assemblies ◽  
Fine Tuning ◽  
Transfer Rates ◽  
Heterogeneous Electron Transfer ◽  
Redox Active ◽  
Kinetics Of ◽  
Fine Tune

Catalysis in confined spaces, such as provided by supramolecular cages, is quickly gaining momentum. It allows for second coordination sphere strategies to control the selectivity and activity of transition metal catalysts, beyond the classical methods like fine-tuning the steric and electronic properties of the coordinating ligands. Only a few electrocatalytic reactions within cages have been reported, and there is no information regarding the electron transfer kinetics and thermodynamics of redox-active species encapsulated into supramolecular assemblies. This contribution revolves around the preparation of M<sub>6</sub>L<sub>12 </sub>and larger M<sub>12</sub>L<sub>24</sub> (M= Pd or Pt) nanospheres functionalized with different numbers of redox-active probes encapsulated within their cavity, either in a covalent fashion via different types of linkers (flexible, rigid and conjugated or rigid and non-conjugated) or by supramolecular hydrogen bonding interactions. The redox-probes can be addressed by electrochemical electron transfer across the rim of nanospheres and the thermodynamics and kinetics of this process are described. Our study identifies that the linker type and the number of redox probes within the cage are useful handles to fine-tune the electron transfer rates, paving the way for the encapsulation of electro-active catalysts and electrocatalytic applications of such supramolecular assemblies.

scholarly journals Modeling Interfacial Electron Transfer in the Double Layer: The Interplay Between Electrode Coupling and Electrostatic Driving

2019 ◽  
Author(s):  
Aditya Limaye ◽  
Adam Willard
Keyword(s):  
Electron Transfer ◽  
Double Layer ◽  
Electrical Potential ◽  
Potential Drop ◽  
Active Species ◽  
Transfer Reactions ◽  
Electronic Coupling ◽  
Interfacial Electron Transfer ◽  
Redox Active ◽  
Solvent Polarization

This manuscript presents a theoretical model for simulating interfacial electron transfer reactions within the electrical double layer. This model resolves the population density of redox active species and simulated electron transfer at the level of Marcus theory, with a fluctuating solvent polarization coordinate. In this model, the kinetics and thermodynamics of electron transfer depend on the values of the electronic coupling of species (to the electrode) and the electrical potential drop, respectively.

scholarly journals Microbial Biofilm Voltammetry: Direct Electrochemical Characterization of Catalytic Electrode-Attached Biofilms

2008 ◽  
Vol 74 (23) ◽  
pp. 7329-7337 ◽  
Author(s):  
Enrico Marsili ◽  
Janet B. Rollefson ◽  
Daniel B. Baron ◽  
Raymond M. Hozalski ◽  
Daniel R. Bond
Keyword(s):  
Electron Transfer ◽  
Quantitative Methods ◽  
Electrochemical Impedance ◽  
Active Species ◽  
Electrochemical Characterization ◽  
Geobacter Sulfurreducens ◽  
Bacterial Cells ◽  
Redox Active

ABSTRACT While electrochemical characterization of enzymes immobilized on electrodes has become common, there is still a need for reliable quantitative methods for study of electron transfer between living cells and conductive surfaces. This work describes growth of thin (<20 μm) Geobacter sulfurreducens biofilms on polished glassy carbon electrodes, using stirred three-electrode anaerobic bioreactors controlled by potentiostats and nondestructive voltammetry techniques for characterization of viable biofilms. Routine in vivo analysis of electron transfer between bacterial cells and electrodes was performed, providing insight into the main redox-active species participating in electron transfer to electrodes. At low scan rates, cyclic voltammetry revealed catalytic electron transfer between cells and the electrode, similar to what has been observed for pure enzymes attached to electrodes under continuous turnover conditions. Differential pulse voltammetry and electrochemical impedance spectroscopy also revealed features that were consistent with electron transfer being mediated by an adsorbed catalyst. Multiple redox-active species were detected, revealing complexity at the outer surfaces of this bacterium. These techniques provide the basis for cataloging quantifiable, defined electron transfer phenotypes as a function of potential, electrode material, growth phase, and culture conditions and provide a framework for comparisons with other species or communities.

scholarly journals Modeling Interfacial Electron Transfer in the Double Layer: The Interplay Between Electrode Coupling and Electrostatic Driving

2019 ◽  
Author(s):  
Aditya Limaye ◽  
Adam Willard
Keyword(s):  
Electron Transfer ◽  
Double Layer ◽  
Electrical Potential ◽  
Potential Drop ◽  
Active Species ◽  
Transfer Reactions ◽  
Electronic Coupling ◽  
Interfacial Electron Transfer ◽  
Redox Active ◽  
Solvent Polarization

This manuscript presents a theoretical model for simulating interfacial electron transfer reactions within the electrical double layer. This model resolves the population density of redox active species and simulated electron transfer at the level of Marcus theory, with a fluctuating solvent polarization coordinate. In this model, the kinetics and thermodynamics of electron transfer depend on the values of the electronic coupling of species (to the electrode) and the electrical potential drop, respectively.

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