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Updated: Dec 30, 2025
Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
A Base-Resistant ZnII -Based Metal-Organic Framework: Synthesis, Structure, Postsynthetic Modification, and Gas
Tao He1, Yong-Zheng Zhang1, Bin Wang1
1Beijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing, 100124, P. R. China.
Abstract:
A ZnII -based metal-organic framework (MOF), [Zn2 (bdp-CHO)2 ]⋅(DMF)(CH3 CN)(H2 O)2 (BUT-31) is reported that was synthesized by the reaction between a newly designed aldehyde-tagged polypyrazole ligand 2,5-di(1H-pyrazol-4-yl)benzaldehyde (H2 bdp-CHO) and a zinc salt. BUT-31 has a unique pillared layered framework structure with 3D intersecting channels approximately 3.4-5.4 Å in size. Powder X-ray diffraction and N2 adsorption experiments revealed that BUT-31 is rigid and permanently porous with the Brunauer-Emmett-Teller surface area of 926 m2 g-1 . Notably, this MOF tolerates boiling water and even highly basic aqueous solution (4 m sodium hydroxide), although dilute acid gradually decomposes its framework. Owing the permanent porosity and chemical stability of BUT-31, covalent post-modification of the free aldehyde group exposed on the pore surface was accomplished by treating the MOF in a concentrated ammonia solution (25 %) at near room temperature, giving rise to an imine-functionalized analogue of BUT-31. Gas adsorption results show that the aldehyde- and imine-functionalized MOFs have high CO2 adsorption capacities, as well as CO2 /N2 and CO2 /CH4 adsorption selectivities.
