Multicenter Electronic Interactions Driving Active Phase Formation in NiFe-MOFs for Anion-Exchange Membrane Water...

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Multimetal doping is crucial for improving oxygen evolution reaction (OER) electrocatalysis, but mechanisms are often unclear.
• Understanding the interplay of dopants is key to designing efficient electrocatalysts.

Purpose of the Study:

• To investigate a novel electronic regulation strategy using orbital complementarity in Ce,Ru-NiFe-MOFs for OER.
• To elucidate the mechanism behind enhanced catalytic activity and durability.

Main Methods:

• Synthesis of Ce,Ru-NiFe-MOFs and characterization using X-ray absorption spectroscopy and HAADF-STEM.
• Density functional theory (DFT) calculations to understand electronic structure and interactions.
• Electrochemical testing for OER performance and durability in alkaline media and anion-exchange membrane water electrolysis.

Main Results:

• Ce/Ru codoping induced multicenter orbital coupling (3d-4d-4f), altering catalyst reconstruction kinetics.
• The optimized catalyst demonstrated an overpotential of 199 mV at 10 mA cm⁻² and exceptional durability (>1600 h at 400 mA cm⁻²).
• Integration into an anion-exchange membrane water electrolysis system achieved 1.747 V at 1000 mA cm⁻² and stable operation.

Conclusions:

• Orbital-level coupling provides a distinct electronic regulation strategy for OER electrocatalysis.
• The study establishes a mechanistic framework linking orbital interactions, catalyst reconstruction, and performance.
• This work offers a general design principle for advanced electrocatalysts via multicenter orbital interactions.