Unlocking the Free Radical Evolution for Directed Conversion of Furoic Acid to 2,5-Furandicarboxylic Acid Over...

Area of Science:

• Catalysis
• Green Chemistry
• Biomass Conversion

Background:

• Efficient synthesis of 2,5-furandicarboxylic acid (FDCA) from biomass is crucial.
• C─H bond activation for furoic acid (FA) carboxylation faces challenges due to conflicting reactivity of furan rings and C─H bonds.

Purpose of the Study:

• To develop a controllable and mild C─H carboxylation process for FA to FDCA.
• To overcome the bottleneck of activating inert C─H bonds under mild conditions.

Main Methods:

• Utilized a high lattice-distorted MnOx catalyst with unique surface trench-like structures.
• Investigated Mn^δ+-O_V-conjugated configurations and electron-rich Mn²⁺ for catalytic activity.
• Explored the free radical evolution process and solvent-polarized CO₂ for carboxylation.

Main Results:

• Achieved high FDCA selectivity of 95.82%.
• Demonstrated efficient carboxylation under mild reaction conditions (≤390 K).
• The catalyst design facilitated FA dehydrogenation and carbon radical reduction.

Conclusions:

• The developed MnOx catalyst enables efficient and mild C─H carboxylation of FA.
• Novel insights into mild activation and conversion of biomass-derived inert chemical bonds were provided.
• This work offers a promising pathway for atom-economical FDCA synthesis.