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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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A Redox-Active Mesoporous Cobalt-Pyrazolate Framework for Reversible O2 Sorption.

Yong-Zheng Zhang1,2, Tao He1, Xiang-Jing Kong1

  • 1Department of Chemical Engineering, College of Materials Science and Engineering, Beijing University of Technology, Beijing, 100124, China.

Angewandte Chemie (International Ed. in English)
|December 24, 2025
PubMed
Summary
This summary is machine-generated.

Researchers developed BUT-45, a novel mesoporous pyrazolate metal-organic framework (MOF). This material exhibits reversible oxygen chemisorption due to its active cobalt sites, advancing MOF design for catalysis and gas storage.

Keywords:
DesymmetrizationMesoporousMetal–organic frameworkPyrazolate ligandReversible O2 adsorption

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Area of Science:

  • Materials Science
  • Chemistry
  • Nanotechnology

Background:

  • Pyrazolate metal-organic frameworks (MOFs) offer superior chemical stability and performance in gas storage, separation, and catalysis compared to carboxylate analogues.
  • Integrating mesoporosity and active sites into pyrazolate MOFs is synthetically challenging due to geometric constraints imposed by M-N bonds.
  • Limited structural diversity in pyrazolate MOFs restricts their potential applications.

Purpose of the Study:

  • To synthesize a mesoporous pyrazolate MOF with integrated active sites.
  • To investigate the oxygen chemisorption properties and reversibility of the new material.
  • To elucidate the mechanism of oxygen binding and release within the MOF structure.

Main Methods:

  • Reticular chemistry was employed to construct the csq-type pyrazolate MOF, BUT-45.
  • Synthesis involved a low-symmetry tetra-pyrazolate ligand (CTP4-) and 8-connected Co6 clusters.
  • Single-crystal X-ray diffraction and in situ spectroscopy were used to analyze the material's structure and oxygen interaction.

Main Results:

  • BUT-45 is the first csq-type mesoporous pyrazolate MOF.
  • The material demonstrates instantaneous and reversible O2 chemisorption at ambient temperature, attributed to active Co sites.
  • Structural analysis revealed the mechanism of Co-O2 adduct formation and its complete reversibility.

Conclusions:

  • Reticular chemistry can successfully map target nets from carboxylate to pyrazolate MOFs, enabling new structures.
  • BUT-45 showcases the potential of pyrazolate MOFs for gas storage and catalysis with enhanced stability.
  • Direct visualization of redox chemistry in MOFs is achieved, offering insights into catalytic mechanisms.