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Tuning Linkers in Azo-Linked Porphyrin-Based Porous Organic Polymers for Enhanced CO₂ Capture.

Matija Popović¹, Tea Frey¹, Mladen Borovina¹

¹University of Zagreb, Faculty of Science, Department of Chemistry, Horvatovac 102a, HR-10000 Zagreb, Croatia.

Langmuir : the ACS Journal of Surfaces and Colloids

|February 1, 2026

Summary

New porous organic polymers (POPs) with azo-linked porphyrin structures were synthesized for effective carbon dioxide (CO2) capture. Linker design significantly impacts CO2 adsorption, demonstrating the importance of chemical environment over surface area alone.

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Area of Science:

Materials Science
Polymer Chemistry
Environmental Science

Background:

Rising atmospheric CO2 concentrations necessitate advanced materials for greenhouse gas capture.
Porous Organic Polymers (POPs) offer tunable properties for CO2 sequestration.
Porphyrin-based POPs are explored for their stability and adsorption potential.

Purpose of the Study:

Synthesize and characterize novel azo-linked porphyrin-based porous organic polymers (APPs).
Investigate the influence of linker chemistry on the porosity and CO2 adsorption capacity of APPs.
Establish structure-property relationships for designing efficient CO2 capture materials.

Main Methods:

Synthesis of four APP variants with varied linkers (APP-BP-OH, APP-AQ, APP-BP-Me, APP-Ph-Me).
Structural confirmation via characterization techniques and thermal stability assessment up to 200 °C.
Gas sorption analysis to determine surface area and CO2 uptake capacities.

Main Results:

APPs exhibit amorphous structures and thermal stability.
APP-Ph-Me shows the highest surface area (673 m2 g-1), while APP-BP-OH achieves higher CO2 uptake (49 mg g-1).
CO2 adsorption is influenced by both surface area and chemical environment, with nitrogen-rich moieties and functional groups playing key roles.

Conclusions:

Linker design critically impacts APP porosity and CO2 adsorption performance.
Nitrogen-rich porphyrin and azo groups are vital for CO2 binding.
Functional groups like hydroxyls enhance adsorption, while steric hindrance can limit it, guiding future POP development for CO2 capture.