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Related Concept Videos

Redox Equilibria: Overview01:23

Redox Equilibria: Overview

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...
Redox Reactions01:24

Redox Reactions

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...
Redox Reactions01:27

Redox Reactions

Redox reactions are vital biochemical processes that underpin energy metabolism in cells. These reactions involve the transfer of electrons between molecules, occurring in tandem as oxidation and reduction. Oxidation refers to the loss of electrons, while reduction denotes their gain. This coupling ensures the seamless flow of electrons through metabolic pathways. For example, in bacterial metabolism, glucose undergoes oxidation to carbon dioxide, while oxygen is simultaneously reduced to...
Redox Titration: Other Oxidizing and Reducing Agents01:26

Redox Titration: Other Oxidizing and Reducing Agents

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...
Balancing Redox Equations02:58

Balancing Redox Equations

Electrochemistry is the science involved in the interconversion of electrical and chemical reactions. Such reactions are called reduction-oxidation, or redox reactions. These important reactions are defined by changes in oxidation states for one or more reactant elements and include a subset of reactions involving the transfer of electrons between reactant species. Electrochemistry as a field has evolved to yield sufficient insights on the fundamental principles of redox chemistry and multiple...
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Updated: May 16, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
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Published on: June 9, 2023

Redox Control in a Conducting MOF through Coupled Electronic-Vibronic Effects.

Darsi Rambabu1, Cristian Morari2, Augustin Ramackers1

  • 1Institute of Condensed Matter and Nanosciences, Université Catholique de Louvain, 1348 Louvain-la-Neuve, Belgium.

Journal of the American Chemical Society
|May 14, 2026
PubMed
Summary

Understanding how cations affect electrically conducting metal-organic frameworks (MOFs) is key. This study reveals that vibrational effects, not just electrostatics, dictate cation influence on redox potentials and conductivity in A2-Mn-DOBDC MOFs.

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Published on: March 18, 2012

Area of Science:

  • Materials Science
  • Electrochemistry
  • Solid-State Chemistry

Background:

  • Electrically conducting metal-organic frameworks (MOFs) are promising for energy storage.
  • Controlling redox properties in MOFs is crucial for their application.
  • Cation intercalation significantly impacts MOF electronic structure and lattice thermodynamics.

Purpose of the Study:

  • To investigate the role of intercalated cations (Li+, Na+, K+) in tuning redox potentials and electronic conductivity of A2-Mn-DOBDC MOFs.
  • To elucidate the interplay between electronic and vibrational contributions to free energy in cation-doped MOFs.
  • To establish a predictive framework for designing conducting MOFs with tailored electrochemical properties.

Main Methods:

  • Finite-temperature free-energy partitioning calculations.
  • Fourier-transform infrared (FTIR) spectroscopy to analyze cation-induced vibrational modes.
  • Density Functional Theory (DFT) calculations of vibrational densities of states.
  • Electrochemical measurements (discharge voltage) of Na2-Mn-DOBDC MOFs.

Main Results:

  • Redox potentials and conductivity ordering (K < Li < Na) contradict simple electrostatic models.
  • Competing electronic (ΔF_EL) and vibrational (ΔF_VIB) free energy terms were identified.
  • ΔF_EL decreases (Li > Na > K), while ΔF_VIB increases (Li < Na < K), with Na showing maximum stabilization.
  • FTIR and DFT confirmed cation-dependent vibrational reorganization.
  • Na2-Mn-DOBDC exhibits a discharge voltage of ~3.0 V vs Na+/Na with retained conductivity.

Conclusions:

  • The nonintuitive redox potential ordering is rationalized by a balance of electronic and vibrational contributions.
  • Vibrational reorganization energy plays a critical role in modulating redox energetics.
  • A general electronic-vibronic route is proposed for tuning redox properties in conducting MOFs.
  • This work provides insights for designing high-performance MOF-based electrochemical devices.