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Redox Reactions01:24

Redox Reactions

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Oxidation-reduction or redox reactions involve the transfer of electrons from one molecule or atom to another. When an atom gains an electron, another atom must lose an electron, meaning oxidation and reduction must occur together. Since the redox occurs in pairs, the atom that gets oxidized is also called the reducing agent or reductant, and the atom that is reduced is also called the oxidizing agent or oxidant. A straightforward way to remember the definitions of oxidation and reduction is...
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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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Ladder Diagrams: Redox Equilibria01:30

Ladder Diagrams: Redox Equilibria

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Ladder diagrams are useful tools for understanding redox equilibrium reactions, especially the effects of concentration changes on the electrochemical potential of the reaction. The vertical axis in the redox ladder diagrams represents the electrochemical potential, E. The area of predominance is demarcated using the Nernst equation.
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Redox Titration: Other Oxidizing and Reducing Agents01:26

Redox Titration: Other Oxidizing and Reducing Agents

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Besides iodine, other oxidizing or reducing agents can serve as titrants in redox titrations. Common oxidizing titrants include KMnO4, cerium(IV), and K2Cr2O7. The choice of oxidizing titrants depends on factors like stability, cost, analyte strength, and reaction rate between the analyte and titrant. KMnO4 is a strong oxidizing titrant that reduces from Mn(VII) to Mn(II) in a highly acidic solution, simultaneously oxidizing the analyte to a higher oxidation state. In this case, KMnO4 acts as a...
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Extraction: Advanced Methods00:56

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Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
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Redox Equilibria: Overview01:23

Redox Equilibria: Overview

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A reduction-oxidation reaction is commonly called a redox reaction. In a redox reaction, electrons are transferred from one species to another rather than being shared between or among atoms. The reducing agent or reductant is the species that loses electrons and gets oxidized in the process. The species that gains electrons and gets reduced in the process is the oxidizing agent or oxidant. Redox reactions are represented as two separate equations called half-reactions, where one equation...
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Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
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A Solid-Solution Approach for Redox Active Metal-Organic Frameworks with Tunable Redox Conductivity.

Gavin S Mohammad-Pour, Kendrich O Hatfield, David C Fairchild

    Journal of the American Chemical Society
    |December 3, 2019
    PubMed
    Summary
    This summary is machine-generated.

    Researchers developed redox-active metal-organic frameworks (MOFs) thin-film electrodes with tunable conductivity. This advancement enables precise control over charge transfer for improved energy and sensing applications.

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    Synthesis and Characterization of Functionalized Metal-organic Frameworks
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    Synthesis and Characterization of Functionalized Metal-organic Frameworks

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    Area of Science:

    • Materials Science
    • Electrochemistry
    • Nanotechnology

    Background:

    • Metal-organic frameworks (MOFs) offer tunable porosity and synthetic control, but their electrochemical applications are limited by conductivity.
    • Systematic tuning of MOF conductivity is crucial for integrating their properties into energy storage and sensing technologies.
    • Redox-active pendants can facilitate charge transfer in MOFs, but controlled integration remains a challenge.

    Purpose of the Study:

    • To introduce a novel strategy for preparing redox-active MOF thin-film electrodes with precisely controlled redox pendant content.
    • To investigate the relationship between redox pendant concentration and the resulting electrical conductivity of MOF electrodes.
    • To assess the electrochemical stability and charge transfer mechanisms within these engineered MOF materials.

    Main Methods:

    • Fabrication of MOF thin-film electrodes using a solid-solution approach with varying ratios of redox-active (alkyl-ferrocene) and inactive linkers.
    • Systematic tuning of redox pendant content during MOF synthesis to control conductivity.
    • Electrochemical characterization, including conductivity measurements and stability testing over thousands of redox cycles.
    • Electroanalytical studies to elucidate charge transfer mechanisms (e.g., diffusion, hopping, percolation).

    Main Results:

    • Successfully prepared MOF thin-film electrodes with tunable redox conductivity.
    • Achieved a maximum electron conductivity of 1.10 mS m-1.
    • Demonstrated excellent crystallographic and electrochemical stability over thousands of redox cycles.
    • Observed solution-like diffusion-controlled conductivity behavior with nonlinear diffusion coefficients.

    Conclusions:

    • The developed strategy enables fine-tuning of redox conductivity in MOFs through controlled incorporation of redox pendants.
    • The MOF electrodes exhibit robust stability and exhibit charge transfer consistent with hopping and percolation models.
    • This work opens new avenues for designing advanced redox-active MOFs for electrochemical devices like batteries and sensors.