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Aromatic π-Electron Density Modulation in Isostructural Metal-Organic Frameworks Enables Efficient Natural Gas Upgrading
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DOI：10.1002/cjoc.70634.png)
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Abstract
En 中文
Efficient separation of C2H6 and C3H8 from CH4 remains a significant challenge due to their similar molecular dimensions and nonpolar nature. This study resolves this bottleneck by realizing π-electron modulation of aromatic pore surfaces via strategic ligand functionalization. Three isostructural metal-organic frameworks with dia topology, namely Ni(3-fpba)2, Ni(3-mpba)2, and Ni(3-npba)2, were synthesized with substituents of varying electronic characters. The progressive enhancement of electron-donating ability systematically enriches the π-electron density, which strengthens C–H···π interactions with alkane molecules in a size-discriminative manner. Notably, the amino-functionalized Ni(3-npba)2 exhibits a C2H6 uptake of 80.5 cm3·g–1 at 273 K and 10 kPa, representing a 96% enhancement over its fluorinated counterpart while maintaining negligible CH4 adsorption. This performance leads to IAST selectivities of 30.4 for C2H6/CH4 and 398 for C3H8/CH4, surpassing most benchmark materials. Dynamic breakthrough experiments and GCMC simulations collectively reveal that enhanced π-electron density intensifies host-guest charge redistribution. These findings establish aromatic π-electron density as a tunable descriptor for the rational design of natural gas purification materials.
Keywords:
Metal–organic framework
Natural gas purification
π-Electron modulation
C–H···π interaction
Isostructural design
Gas adsorption
Dynamic separation
Crystal engineering
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