Valence-tuned electron bridge enables high-yield multi-electron HMF oxidation over spinel catalysts

Area of Science:

• Materials Science
• Catalysis
• Green Chemistry

Background:

• The conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is crucial for producing bio-based plastics.
• Current catalytic methods face challenges due to slow multi-electron transfer kinetics.

Purpose of the Study:

• To engineer a novel electron bridge in spinel CoMn2O4 to enhance electron transfer kinetics for HMF oxidation.
• To improve the efficiency and yield of FDCA production.

Main Methods:

• Synthesis of spinel CoMn2O4 with a precisely regulated Mn-O-Co electron bridge.
• Experimental characterization (e.g., spectroscopy, diffraction) and theoretical calculations (e.g., DFT) to analyze electronic structure and electron transfer pathways.

Main Results:

• An efficient Mn4+-O2--Co3+ electron bridge was successfully engineered, enhancing electron delocalization and mobility.
• The electron bridge facilitated cooperative six-electron transfer in HMF oxidation via a dynamic electron compensation mechanism.
• Achieved a high yield of 98.1% for 2,5-furandicarboxylic acid.

Conclusions:

• The engineered electron bridge provides a theoretical basis for understanding cooperative electron transfer in heterogeneous catalysis.
• This strategy offers a rational approach for designing advanced catalysts for efficient bio-based chemical production.