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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.
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Proton-Conductive Cerium-Based Metal-Organic Frameworks.

Wei Huan Ho1, Shih-Cheng Li2, Yi-Ching Wang1

  • 1Department of Chemical Engineering, National Cheng Kung University, Tainan City 70101, Taiwan.

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Summary

Cerium-based metal-organic frameworks (MOFs) show enhanced proton conductivity. Replacing zirconium with cerium in MOF-808 nodes lowers activation energy, making them promising for energy applications.

Keywords:
bimetallic MOFcerium-based MOFfuel cellmix-metal nodeproton conductionzirconium-based MOF

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Area of Science:

  • Materials Science
  • Chemistry
  • Energy Storage

Background:

  • Proton conductivity in metal-organic frameworks (MOFs) is crucial for energy applications.
  • Zirconium-based MOFs are commonly studied, but alternative materials are needed.
  • Understanding structure-property relationships is key to designing efficient proton conductors.

Purpose of the Study:

  • To investigate proton-conducting behaviors of cerium-based MOFs (Ce-MOF-808) and compare them to zirconium-based counterparts.
  • To explore the effect of substituting zirconium with cerium on proton conductivity and activation energy.
  • To assess the potential of cerium-based MOFs for future energy-related applications.

Main Methods:

  • Synthesis and characterization of Ce-MOF-808, isostructural Zr-MOF-808, and bimetallic MOFs.
  • Measurement of proton conductivity (σ) under varying humidity and temperature conditions.
  • Density functional theory (DFT) calculations to probe proton affinities.

Main Results:

  • Substitution of Zr with Ce in MOF-808 nodes significantly increased proton conductivity.
  • Ce-MOF-808 exhibited a conductivity of 4.4 × 10⁻³ S/cm at 25 °C and 99% relative humidity.
  • A low activation energy (Ea) of 0.14 eV was achieved for Ce-MOF-808, among the lowest reported for proton-conductive MOFs.

Conclusions:

  • Cerium-based MOFs, specifically Ce-MOF-808, demonstrate superior proton conductivity compared to their zirconium-based analogs.
  • The low activation energy suggests efficient proton transport mechanisms in cerium-based MOFs.
  • Cerium-based MOFs represent a promising platform for designing advanced proton conductors for energy applications.