Photoactive Heteropore Covalent Metal-Organic Frameworks for CO2 Photoreduction

Area of Science:

• Materials Science
• Catalysis
• Photochemistry

Background:

• Metal-organic frameworks (MOFs) are recognized for their potential in photocatalytic CO2 reduction (CO2RR).
• Existing strategies focus on enhancing MOF photocatalytic activity, but photoactive heteropore MOFs for CO2RR are underexplored.

Purpose of the Study:

• To synthesize and investigate 2D copper cyclic trinuclear unit (Cu-CTU)-based heteropore covalent MOFs (CMOFs) for photocatalytic CO2RR.
• To evaluate the impact of heteropore structures and photosensitive units on CO2 uptake and photocatalytic performance.

Main Methods:

• Synthesis of two 2D heteropore CMOFs and two homopore analogues based on Cu-CTU.
• Characterization of CO2 uptake capacity and photocatalytic CO2RR performance.
• Evaluation of selectivity and apparent quantum yield (AQY) under specific conditions.

Main Results:

• Heteropore CMOFs exhibited double the CO2 uptake compared to homopore analogues.
• Incorporation of photosensitive units enhanced light harvesting and charge separation.
• Achieved a CO generation rate of 3548 μmol g-1 h-1 with 94.7% selectivity and 6.78% AQY at 420 nm.
• Demonstrated high photocatalytic activity under diluted CO2 and natural sunlight.

Conclusions:

• Heteropore structures and photosensitive units synergistically boost MOF photocatalytic CO2RR performance.
• The developed photoactive heteropore CMOFs show significant promise for efficient CO2 conversion.
• This study highlights a novel strategy for designing advanced MOF catalysts for CO2 utilization.