Electrostatic complementarity and interlayer coupling modulation in halogen-modified covalent organic frameworks for...

Area of Science:

• Materials Science
• Catalysis
• Nanotechnology

Background:

• Covalent organic frameworks (COFs) show potential for solar-driven hydrogen peroxide (H2O2) synthesis.
• Current limitations include inefficient charge transfer and O2 adsorption.

Purpose of the Study:

• To develop a halogen-functionalized COF material for improved solar-driven H2O2 photosynthesis.
• To investigate the role of halogen functionalization in enhancing charge transport and O2 adsorption.

Main Methods:

• Synthesis of halogen-functionalized COFs (F-COF, Cl-COF, Br-COF).
• Density Functional Theory (DFT) calculations to analyze electronic structure and orbital overlap.
• Evaluation of catalytic performance for H2O2 production.

Main Results:

• Halogen functionalization, particularly with fluorine (F-COF), enhances interlayer π-π coupling and creates an electron transport bridge.
• DFT calculations reveal increased π-orbital delocalization and interlayer orbital overlap in the order F-COF > Cl-COF > Br-COF > H-COF.
• Halogen-induced electronic polarization improves O2 adsorption through complementary charge distribution.
• F-COF achieved a high catalytic rate of 2547.7 μmol g⁻¹ h⁻¹ and 10.2% quantum efficiency.

Conclusions:

• Halogen-functionalized COFs offer a novel strategy for optimizing electronic distribution in materials.
• This approach effectively regulates charge transport and O2 adsorption sites for enhanced photocatalytic performance.
• The study provides a new pathway for designing advanced COFs for solar fuel applications.