Stepwise Engineering the Pore Aperture of a Cage-like MOF for the Efficient Separation of Isomeric C4 Paraffins under Humid Conditions.
Lu WangWenjuan XueHejin ZhuXiangyu GuoHongliang HuangChongli ZhongPublished in: Angewandte Chemie (International ed. in English) (2023)
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-C 4 H 10 uptake. Notably, the resulting Zn-bzc-2CH 3 (bzc-2CH 3 =3,5-dimethylpyrazole-4-carboxylic acid) can sensitively capture n-C 4 H 10 and exclude iso-C 4 H 10 , affording molecular-sieving for n-C 4 H 10 /iso-C 4 H 10 separation and high n-C 4 H 10 adsorption capacity (54.3 cm 3 g -1 ). Breakthrough tests prove n-C 4 H 10 /iso-C 4 H 10 can be efficiently separated and high-purity iso-C 4 H 10 (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-2CH 3 is a new benchmark adsorbent for n-C 4 H 10 /iso-C 4 H 10 separation.