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Synthesis and Characterization of Functionalized Metal-organic Frameworks

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Solvent-Driven Dynamics: Crafting Tailored Transformations of Cu(II)-Based MOFs.

Cheol Yeong Heo¹, Mariana L Díaz-Ramírez^1,2, Sun Ho Park¹

¹Department of Physics and Chemistry, DGIST, Daegu 42988, Korea.

ACS Applied Materials & Interfaces

|February 12, 2024

Summary

Interpenetrated metal-organic frameworks (MOFs) show enhanced ethane and ethylene uptake due to smaller pores. Controlled MOF transformations are key for selective gas capture and separation applications.

Keywords:

Cu-based paddlewheel MOF DUT-34 MOF-14 MOF-143 deinterpenetration ethane capture ethane/ethylene separation ethylene capture reversible interpenetration

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Area of Science:

Materials Science
Chemistry
Chemical Engineering

Background:

Metal-organic frameworks (MOFs) are crystalline porous polymers studied for gas uptake.
Interpenetrated MOFs offer enhanced stability and smaller micropores for capturing nonpolar molecules.
Ethane/ethylene separation is a critical industrial process.

Purpose of the Study:

To explore solvent-assisted reversible interpenetration and deinterpenetration of a Cu(II)-based MOF.
To investigate the adsorptive separation of ethane and ethylene using these MOFs.
To identify factors influencing gas uptake and selectivity in MOFs.

Main Methods:

Solvent-assisted synthesis and transformation of MOF-143 (noninterpenetrated) and MOF-14 (doubly interpenetrated).
Utilized protic solvents (water, methanol, ethanol) for interpenetration and pyridine for deinterpenetration.
Gas adsorption/desorption experiments to evaluate ethane and ethylene uptake and selectivity.

Main Results:

Interpenetrated MOF-14 showed higher ethane and ethylene uptakes than noninterpenetrated MOF-143 due to narrower micropores.
Pristine MOF-14 exhibited higher ethane selectivity than MOF-14 derived from MOF-143.
The 'fraction of micropore volume' was identified as a critical factor for ethane uptake.

Conclusions:

Controlled interpenetration and deinterpenetration of MOFs via solvent-assisted strategies are feasible.
Interpenetrated MOFs with narrower micropores are promising for selective nonpolar gas capture.
Optimizing MOF crystal size, micropore characteristics, and crystallinity is crucial for efficient gas separation.