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Free-energy diagrams, or reaction coordinate diagrams, are graphs showing the energy changes that occur during a chemical reaction. The reaction coordinate represented on the horizontal axis shows how far the reaction has progressed structurally. Positions along the x-axis close to the reactants have structures resembling the reactants, while positions close to the products resemble the products.  Peaks on the energy diagram represent stable structures with measurable lifetimes, while...
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High thermal stability of core-shell structures dominated by negative interface energy.

Yong-Fu Zhu1, Ning Zhao1, Bo Jin1

  • 1Key Laboratory of Automobile Materials, Ministry of Education, and School of Materials Science and Engineering, Jilin University, Changchun 130022, China. jiangq@jlu.edu.cn.

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Nanoscale core-shell structures exhibit enhanced thermal stability due to core superheating, influenced by interface energies. This finding aids in designing superior catalysts.

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Catalysis

Background:

  • Nanoscale core/shell structures offer superior catalytic properties.
  • Understanding their thermal stability is crucial for catalytic applications.

Purpose of the Study:

  • To thermodynamically investigate the thermal stability of coherent core-shell structures.
  • To analyze the impact of core and shell melting points on stability.

Main Methods:

  • Thermodynamic analysis of core-shell structures.
  • Consideration of core and shell bulk melting points (Tm(∞)).
  • Evaluation of interface energies (solid-solid and solid-liquid).

Main Results:

  • Core-shell structures with low-Tm(∞) cores exhibit superheating, preventing premature melting.
  • High-Tm(∞) shells can trigger core melting in small core structures.
  • Negative solid-solid interface energy contributes to core superheating.
  • Positive solid-liquid interface energy drives melting point depression.
  • Low-Tm(∞)-core structures show reduced thermal expansion mismatch, higher diffusion activation energy, and lower heat capacity.

Conclusions:

  • The presence of negative interface energy enhances the thermal stability of core-shell structures.
  • These findings are beneficial for designing advanced core-shell catalysts.