Stepwise Engineering the Pore Aperture of a Cage‐like MOF for the Efficient Separation of Isomeric C4 Paraffins under Humid Conditions

The separation of isomeric C4 paraffins is an important task in the petrochemical industry, while current adsorbents undergo a trade-off relationship between selectivity and adsorption capacity. In this work, the pore aperture of a cage-like Zn-bzc (bzc=pyrazole-4-carboxylic acid) is tuned by the stepwise installation methyl groups on its narrow aperture to achieve both molecular-sieving separation and high n-C₄ H₁₀ uptake. Notably, the resulting Zn-bzc-2CH₃ (bzc-2CH₃ =3,5-dimethylpyrazole-4-carboxylic acid) can sensitively capture n-C₄ H₁₀ and exclude iso-C₄ H₁₀ , affording molecular-sieving for n-C₄ H₁₀ /iso-C₄ H₁₀ separation and high n-C₄ H₁₀ adsorption capacity (54.3 cm³ g^-1 ). Breakthrough tests prove n-C₄ H₁₀ /iso-C₄ H₁₀ can be efficiently separated and high-purity iso-C₄ H₁₀ (99.99 %) can be collected. Importantly, the hydrophobic microenvironment created by the introduced methyl groups greatly improves the stability of Zn-bzc and significantly eliminates the negative effect of water vapor on gas separation under humid conditions, indicating Zn-bzc-2CH₃ is a new benchmark adsorbent for n-C₄ H₁₀ /iso-C₄ H₁₀ separation.