Precisely Embedding Active Sites into a Mesoporous Zr-Framework through Linker Installation for High-Efficiency...

Area of Science:

• Materials Science
• Nanotechnology
• Catalysis

Background:

• Microporous metal-organic frameworks (MOFs) have been widely studied for pore engineering.
• Achieving MOFs with both specific pore sizes and desired functionalities remains challenging.
• Small pore sizes in many MOFs limit their practical applications.

Purpose of the Study:

• To design and synthesize a mesoporous MOF (PCN-808) suitable for post-synthetic modification.
• To introduce a ruthenium-based metalloligand into the MOF structure.
• To evaluate the photocatalytic performance of the modified MOF (PCN-808-BDBR).

Main Methods:

• Synthesis of a mesoporous MOF, PCN-808, using Zr6 clusters and tetratopic carboxylate ligands.
• Post-synthetic modification of PCN-808 by installing a linear ruthenium-based metalloligand into its channels.
• Photocatalytic testing of the modified MOF (PCN-808-BDBR) in the aza-Henry reaction and dihydroartemisinic acid oxidation.

Main Results:

• Successful synthesis of PCN-808, a mesoporous MOF with accessible metal sites and framework flexibility.
• Precise installation of a ruthenium-based metalloligand into PCN-808, yielding PCN-808-BDBR, while preserving mesoporosity.
• PCN-808-BDBR demonstrated high conversion yields in the aza-Henry reaction over six cycles and exceptional yields in dihydroartemisinic acid oxidation.

Conclusions:

• PCN-808 serves as an effective scaffold for post-synthetic modification due to its accessible sites and flexibility.
• The resulting mesoporous MOF, PCN-808-BDBR, exhibits significant potential as a photocatalyst for organic synthesis.
• The mesoporous nature is crucial for the high efficiency observed in the tested photocatalytic reactions.