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Customizable Aperture Geometry in Metal-Organic Frameworks for Kinetic Hydrocarbon Separation.

Shengyi Su^1,2, Haomiao Xie^1,2, Bang Hou^1,2

¹Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.

Journal of the American Chemical Society

|October 8, 2025

Summary

This summary is machine-generated.

Researchers developed new metal-organic frameworks (MOFs) using a mixed-linker strategy to precisely control pore size for efficient hydrocarbon separations. These novel MOFs, NU-415 and NU-416, show enhanced selectivity and capacity for separating hexane isomers.

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Area of Science:

Materials Science
Chemical Engineering
Nanotechnology

Background:

Precise control of pore dimensions in metal-organic frameworks (MOFs) is vital for optimizing hydrocarbon separations, influencing selectivity, capacity, diffusion, and recyclability.
While MOFs allow pore environment tuning, customizing aperture geometry for kinetic separation performance remains a significant challenge.

Purpose of the Study:

To develop isoreticular multivariate MOFs (NU-415 and NU-416) with tailored aperture geometries for enhanced kinetic separation of hexane isomers.
To demonstrate the efficacy of a mixed-linker synthesis strategy for precise pore architecture control in MOFs.

Main Methods:

Employed a mixed-linker synthesis strategy combining long and short linkers on fcu-net Zr-MOFs.
Constructed NU-415 and NU-416 with modified, isosceles triangular apertures.
Utilized sorption, liquid batch separation, and X-ray diffraction measurements for performance evaluation.

Main Results:

NU-415 and NU-416 exhibited significantly improved selectivity, capacity, stability, and recyclability compared to existing MOFs.
Achieved high uptake capacities (2.2 mmol g-1 in 1 min) and excellent n-hexane to 2,2-dimethylbutane selectivity (>200) in ternary mixtures.
Confirmed that separation performance is primarily driven by kinetic differences.

Conclusions:

The mixed-linker synthesis strategy enables precise and predictable control over MOF pore architecture.
NU-415 and NU-416 demonstrate superior performance for linear to monobranched hexane isomer separation.
This approach offers a promising solution for advanced adsorptive separation applications.