Structurally Locked Cobalt-Metalated Covalent Organic Frameworks for Enhanced Photocatalytic CO₂ Reduction

Area of Science:

• Materials Science
• Catalysis
• Photochemistry

Background:

• Developing efficient metal-based covalent organic frameworks (COFs) for photocatalytic CO2 reduction is crucial.
• Traditional metallization methods suffer from poor charge separation efficiency in these materials.

Purpose of the Study:

• To synthesize structurally locked metal-COFs with improved charge separation and catalytic activity.
• To investigate the mechanism of photocatalytic CO2 reduction using computational methods.

Main Methods:

• Anchoring metallic catalytic sites into COFs to create BTT-Co-COF and BTT-Ni-COF.
• Evaluating photocatalytic CO2 reduction performance, including CO production rate and selectivity.
• Employing density functional theory (DFT) calculations to study the reaction mechanism.

Main Results:

• BTT-Co-COF and BTT-Ni-COF exhibit enhanced structural rigidity and charge separation efficiency.
• BTT-Co-COF achieved a CO production rate of 12.2 mmol gcat-1 h-1 with 93% selectivity.
• BTT-Co-COF significantly outperformed BTT-Ni-COF (5.5 mmol gcat-1 h-1) and the parent BTT-COF (1.1 mmol gcat-1 h-1).

Conclusions:

• Structurally locked metal-COFs provide an effective strategy for efficient photocatalytic CO2 reduction.
• This approach enhances structural integrity and charge separation, leading to improved catalytic performance.
• The developed metal-COFs are promising for the highly efficient production of syngas from CO2.