Modulating the Electronic Structures of Dual-Atom Catalysts via Coordination Environment Engineering for Boosting CO₂...

Area of Science:

• Electrochemistry
• Materials Science
• Catalysis

Background:

• Dual-atom catalysts (DACs) leverage synergistic effects between adjacent metal sites for enhanced catalytic activity.
• Optimizing the electronic structure of DACs is crucial for improving their performance in reactions like CO2 reduction, but remains a significant challenge.

Purpose of the Study:

• To investigate the impact of varying coordination environments on the electronic structure of Ni2 dual-atom catalysts.
• To identify a Ni2 DAC with superior electrocatalytic activity for CO2 reduction.

Main Methods:

• Synthesis and characterization of three Ni2 DACs with different coordination environments (Ni2-N7, Ni2-N5C2, Ni2-N3C4).
• Electrocatalytic evaluation of the synthesized DACs for CO2 reduction.
• Density functional theory (DFT) calculations to elucidate structure-activity relationships.

Main Results:

• The Ni2-N3C4 DAC demonstrated significantly enhanced electrocatalytic activity for CO2 reduction compared to single-atom Ni catalysts and other Ni2 DACs.
• Electronic structure modulation of the Ni center was achieved by altering the coordination environment.
• DFT calculations confirmed that optimized binding energies for COOH* and CO* intermediates contribute to the high activity of Ni2-N3C4.

Conclusions:

• Coordination environment engineering is an effective strategy for tuning the electronic structure of Ni2 DACs.
• The Ni2-N3C4 catalyst exhibits excellent potential for efficient CO2 electroreduction.
• Understanding the intermediate binding energies provides insights into designing high-performance electrocatalysts.