Porous Organic Polymers with Azo, Azoxy, and Azodioxy Linkages: Design, Synthesis, and CO₂ Adsorption Properties

Area of Science:

• Materials Science
• Chemical Engineering
• Environmental Science

Background:

• Rising atmospheric CO2 necessitates advanced adsorbents for carbon capture.
• Porous organic polymers (POPs) offer tunable properties for CO2 separation.
• Nitrogen-nitrogen (N-N) linked POPs are explored for their CO2 adsorption capabilities.

Purpose of the Study:

• To review experimental and computational studies on N-N linked POPs for CO2 capture.
• To emphasize the influence of synthesis, building blocks, and topology on CO2 uptake.
• To provide guidelines for designing POPs with enhanced CO2 adsorption.

Main Methods:

• Summarizing experimental findings on azo-linked POPs and related N-N systems.
• Reviewing computational workflows including DFT, GCMC simulations, and binding energy calculations.
• Analyzing structure-property relationships for CO2 adsorption in POPs.

Main Results:

• Synthetic routes, building blocks, and framework topology significantly impact CO2 uptake in N-N linked POPs.
• Reversible nitroso/azodioxide chemistry presents a pathway to ordered porous materials.
• Computational models effectively rationalize adsorption behavior and identify favorable binding sites.
• Pore accessibility and stacking significantly influence predicted CO2 adsorption.

Conclusions:

• N-N linked POPs are promising for CO2 capture, with tunable properties.
• Computational approaches are crucial for understanding and designing these materials.
• Further research is needed to overcome challenges and optimize POPs for efficient CO2 adsorption.