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In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
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Substrate suppression of oxidation process in pnictogen monolayers.

Rafael L H Freire1, F Crasto de Lima1, A Fazzio1

  • 1Ilum School of Science, Brazilian Center for Research in Energy and Materials (CNPEM), Campinas, SP, Brazil. felipe.lima@ilum.cnpem.br.

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Summary

Investigating oxidation in 2D materials like arsenic, antimony, and bismuth revealed that a silicon carbide (SiC) substrate significantly slows down oxidation compared to freestanding layers. Spin-orbit coupling also impacts oxidation mechanisms and timescales.

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Area of Science:

  • Materials Science
  • Condensed Matter Physics
  • Computational Chemistry

Background:

  • Two-dimensional (2D) materials offer unique properties for advanced device applications.
  • Oxidation significantly alters the electronic and chemical properties of 2D materials, necessitating a thorough understanding.
  • Pnictogen monolayers (As, Sb, Bi) are promising 2D materials, but their stability against oxidation is crucial.

Purpose of the Study:

  • To investigate the oxidation mechanisms and energy barriers of freestanding and SiC-supported As, Sb, and Bi monolayers.
  • To explore the influence of spin-orbit coupling and substrate effects on the oxidation process.
  • To determine the role of O2 spin-state transitions in the oxidation of these 2D materials.

Main Methods:

  • Utilized *ab initio* calculations to simulate oxidation processes.
  • Incorporated Landau-Zener transition theory to account for O2 spin-state transitions.
  • Calculated oxidation energy barriers and analyzed the impact of spin-orbit coupling.

Main Results:

  • The presence of a SiC substrate substantially reduces the oxidation timescale compared to freestanding monolayers.
  • Oxidation energy barriers exhibit a trend: decreasing from As to Sb to Bi for freestanding systems, but increasing for SiC-supported systems.
  • Spin-orbit coupling plays a significant role in the oxidation mechanisms, affecting the overall timescales.

Conclusions:

  • SiC-supported pnictogen monolayers demonstrate enhanced robustness against oxidation compared to their freestanding counterparts.
  • The findings provide critical insights into the stability and potential applications of 2D pnictogens in device technologies.
  • Understanding oxidation pathways, including spin dynamics and substrate interactions, is essential for designing stable 2D material-based devices.