Control of CO₂ Electrocatalysis via Modularly Customizable Graphdiyne

Area of Science:

• Materials Science
• Catalysis
• Nanotechnology

Background:

• Tailoring material properties at the atomic level is crucial for advanced applications.
• Conventional materials often lack design flexibility, limiting performance optimization.
• Modular graphdiyne (GDY) offers a configurable platform for precise molecular engineering.

Purpose of the Study:

• To establish a chemically guided molecular design framework for atomic-level control of catalytic behaviors.
• To systematically investigate the relationship between molecular structure and catalytic function in GDYs.
• To develop a predictive model for optimizing CO2 reduction (CO2RR) and syngas production.

Main Methods:

• Utilized density functional theory (DFT) calculations and experimental validation.
• Synthesized 13 organic molecular units with electron-donating/withdrawing groups to create customizable GDYs.
• Correlated electronic descriptors (work function, VBM, Fermi level) with catalytic activity.

Main Results:

• Identified a volcano-shaped correlation between alkyne carbon oxidation state and CO2RR activity.
• Established a predictive framework linking electronic properties to catalytic performance.
• Achieved tunable CO/H2 ratios (1:10 to 13:1) and high CO selectivity (93% Faradaic efficiency) with a fluorinated GDY (3FGDY).

Conclusions:

• Demonstrated atomic-level structure-performance relationships in modular GDY materials.
• Provided a robust proof-of-concept for designing customizable catalysts.
• Highlighted the potential for GDYs in efficient syngas production and sustainable energy conversion.