Engineering Gradient D-d Orbital Occupancy to Boost Substrate Adsorption for Efficient Electrocatalytic Biomass...

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Electrocatalysis offers a sustainable route for biomass upgrading.
• 5-hydroxymethylfurfural (HMF) conversion to 2,5-furandicarboxylic acid (FDCA) is key for polymer production.
• Tuning catalyst electronic structure is vital for efficient HMF electrooxidation.

Purpose of the Study:

• To investigate the effect of Mn modification on Ni-based electrocatalysts for HMF electrooxidation.
• To understand the relationship between electronic structure (electron gradient orbitals, spin state) and catalytic activity.
• To achieve high current density and stable FDCA production.

Main Methods:

• Synthesis of Mn-modified porous metallic skeleton Ni electrocatalysts.
• Electrochemical characterization of catalysts for HMF electrooxidation.
• Analysis of electronic structure and its correlation with catalytic performance.
• Continuous flow electrolysis experiments for stability assessment.

Main Results:

• Mn introduction weakens e-e repulsion via π-donation, tuning the electronic structure.
• Achieved ultra-high current density of 1.2 A cm⁻² at 1.42 V vs RHE for HMF electrooxidation.
• Demonstrated stable FDCA production with 88.3% yield after ~300 h in continuous flow electrolysis.

Conclusions:

• The electron gradient orbitals-activity relationship provides guidance for designing efficient electrocatalysts.
• Mn-modified Ni catalysts show significant potential for sustainable biomass upgrading.
• This work advances the electrocatalytic conversion of HMF to FDCA for polymer applications.