Enhanced p-p orbital coupling for efficient CO₂-to-formate conversion via counterion-induced amorphization strategy...

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Electrocatalytic reduction of carbon dioxide (CO2) is crucial for carbon neutrality.
• Indium-based materials show promise for CO2 electroreduction but require optimization.
• Anionic metal-organic frameworks (MOFs) offer tunable properties for catalysis.

Purpose of the Study:

• To develop a novel catalyst for efficient CO2 electroreduction to formate.
• To investigate the effect of counterion-induced amorphization on catalyst performance.
• To understand the mechanism behind enhanced CO2 electroreduction activity.

Main Methods:

• Synthesis of anionic indium metal-organic frameworks (In-MOFs).
• Counterion exchange to induce framework amorphization.
• Electrochemical testing for CO2 reduction to formate.
• In-situ experimental and theoretical studies (e.g., DFT) to elucidate reaction mechanisms.

Main Results:

• Amorphous In-MOF (A-In(OH)x(CO3)y) achieved 97.2% Faradaic efficiency for formate production at -1.4 V vs. RHE.
• The catalyst demonstrated high stability, maintaining ~90% selectivity for 36 hours.
• Amorphization enhanced intermediate binding through strong In p-O p orbital coupling, lowering activation energy.

Conclusions:

• Counterion-induced amorphization is an effective strategy to create high-performance CO2 electroreduction catalysts.
• The amorphous In-MOF catalyst significantly improves formate selectivity and stability.
• This approach unlocks p-orbital activity for efficient CO2 conversion, contributing to carbon neutrality goals.