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<p>Single-atom-modified graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) has shown significant advantages in the photoactivation small-molecule. However, the precise role of single-atom Fe in O<sub>2</sub> activation remains to be further explored. Herein, theoretical calculations were conducted to investigate the mechanism of O<sub>2</sub> activation in single-atom Fe-modified carbon nitride (SA-CN). The results reveal that the C/N framework (Site 1) adjacent to the Fe–N<sub>4</sub> center serves as the only efficient O<sub>2</sub> activation site, while the Fe–N<sub>4</sub> center (site 4) acts as a hole acceptor due to the excessive O<sub>2</sub> reduction effect. It is revealed that the high activity of Site 1 is attributed to the synergistic mechanism of ground-state pre-polarization and excited-state orbital reorganization, while the Fe–N<sub>4</sub> center lies in modulating the local coordination environment to endow the adjacent inert framework with enhanced electron-donating capability, thereby exerting an indirect regulatory role. These findings clarify the intrinsic functions between the metal center and ligand sites in single-atom photocatalytic system, providing an important theoretical basis for the rational design of high-performance photocatalysts.</p> Graphical Abstract <p></p>

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Theoretical Insights into the Role of Single-Atom-Modified Carbon Nitride in Photoactivation O2: The Indirect Regulatory Effect of the Fe–N4 Center

  • 期刊论文

  • 发表日期：

    2026年6月17日

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  • Hao Yang,
  • Chenggang Jia,
  • Kai Hou,
  • Jinming Ye,
  • Jun Luo

摘要

Single-atom-modified graphitic carbon nitride (g-C3N4) has shown significant advantages in the photoactivation small-molecule. However, the precise role of single-atom Fe in O2 activation remains to be further explored. Herein, theoretical calculations were conducted to investigate the mechanism of O2 activation in single-atom Fe-modified carbon nitride (SA-CN). The results reveal that the C/N framework (Site 1) adjacent to the Fe–N4 center serves as the only efficient O2 activation site, while the Fe–N4 center (site 4) acts as a hole acceptor due to the excessive O2 reduction effect. It is revealed that the high activity of Site 1 is attributed to the synergistic mechanism of ground-state pre-polarization and excited-state orbital reorganization, while the Fe–N4 center lies in modulating the local coordination environment to endow the adjacent inert framework with enhanced electron-donating capability, thereby exerting an indirect regulatory role. These findings clarify the intrinsic functions between the metal center and ligand sites in single-atom photocatalytic system, providing an important theoretical basis for the rational design of high-performance photocatalysts.

Graphical Abstract