Transforming zirconium-porphyrin frameworks into 2D nanosheet-assembled architectures for enhanced carbon dioxide capture.

Developing advanced sorbents for selective carbon dioxide (CO 2) sequestration with minimal energy consumption remains a pivotal challenge. This study presents a novel strategy through transforming 3D bulk zirconium-porphyrin frameworks into the corresponding 2D nanosheet-assembled superstructures for enhanced CO 2 capture. The hierarchical frameworks with well-organized nanosheet architectures exhibit significantly increased specific surface area from 600 m²/g to 2400 m²/g while providing kinetic benefits for gas diffusion. Compared to the adsorption behavior of the bulk counterparts, the nanosheet-assembled frameworks demonstrate a 1.5-fold increase in CO 2 adsorption capacity without compromising CO 2 /N 2 selectivity. Theoretical calculation reveals that the coordination unsaturated Zr-O clusters, electron delocalized environments both in interlayer gaps and micropores provided binding sites for CO 2 capture. Our research demonstrates an adaptable structure-directed approach for the crystal engineering of metal-organic frameworks which would inspire the creation of state-of-the-art crystalline porous materials for broadened applications. [Display omitted] Transforming 3D zirconium-porphyrin frameworks into 2D nanosheet-assembled superstructures enabling enhanced CO 2 adsorption capacity while providing kinetic benefits in gas diffusion. The 2D superstructures exhibited increased CO 2 adsorption capacity by 2.5 times compared to the bulk counterparts without sacrificing the CO 2 /N 2 selectivity. • A strategy to fabricate nanosheet-assembled zirconium-porphyrin superstructures. • Significantly increased specific surface area up to 2400 m²/g. • Enhanced CO 2 capture ability without compromising CO 2 /N 2 selectivity. • Theoretical calculation revealing the CO 2 adsorption mechanism. [ABSTRACT FROM AUTHOR]