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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...
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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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Geminal Cl-Bridged Dual-Fe-Atom Catalyst for Efficient and Stable Oxygen Reduction Reaction.

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Researchers developed a stable dual-iron atom catalyst by understanding iron-nitrogen-carbon catalyst degradation. This new catalyst shows remarkable durability for the oxygen reduction reaction (ORR) in batteries.

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Area of Science:

  • Electrochemistry
  • Materials Science
  • Catalysis

Background:

  • Atomically dispersed iron-nitrogen-carbon (Fe-N-C) catalysts are promising for the oxygen reduction reaction (ORR).
  • Structural instability and iron demetallization limit the practical application of Fe-N-C catalysts.
  • Understanding the degradation mechanism is crucial for designing robust catalysts.

Purpose of the Study:

  • To elucidate the mechanism of electrochemical degradation in Fe-N-C catalysts during ORR.
  • To design and synthesize a novel dual-Fe-atom catalyst with enhanced structural stability.
  • To investigate the role of catalyst structure in ORR performance and durability.

Main Methods:

  • Mechanistic studies to identify the cause of Fe demetallization.
  • Synthesis of a dual-Fe-atom catalyst with a N3-Fe-Cl-Fe-N3 structure.
  • Theoretical calculations and experimental validation (electrochemical testing, durability cycling, zinc-air battery performance).

Main Results:

  • Electrochemical degradation of Fe-N-C catalysts is linked to a dynamic disparity between Fe-N and Fe-O bonds, causing Fe demetallization.
  • The synthesized dual-Fe-atom catalyst exhibits a unique N3-Fe-Cl-Fe-N3 structure.
  • The bridging Cl atom regulates electronic structure, enhancing Fe-N and Fe-Cl bond stability and attenuating Fe-O interactions during ORR.
  • The catalyst demonstrated exceptional ORR stability, minimal Fe leaching (16.4 μg L-1 after 20000 cycles), retained 88% current over 160 h, and provided over 1000 h of stable performance in a zinc-air battery.

Conclusions:

  • The study reveals the mechanism of Fe demetallization in Fe-N-C catalysts under ORR conditions.
  • A dual-Fe-atom catalyst with a reinforced structure offers superior electrochemical robustness and durability.
  • This work provides insights for designing highly stable, noble-metal-free ORR electrocatalysts.