Trans-/cis-olefin isomers play a vital role in the petrochemical industry. The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties. Herein, two new tailor-made anion-pillared ultramicroporous metal–organic frameworks (MOFs), ZU-36-Ni and ZU-36-Fe (GeFSIX-3-Ni and GeFSIX-3-Fe) are reported for the first time for the efficient trans-/cis-2-butene (trans-/cis-C4H8) mixture splitting by enhanced molecular exclusion. Notably, ZU-36-Ni unexpectedly exhibited smart guest-adaptive pore channels for trapping trans-C4H8 with a remarkable adsorption capacity (2.45 mmol·g-1) while effectively rejecting cis-C4H8 with a high purity of 99.99％. The dispersion-corrected density functional theory (DFT-D) calculation suggested that the guest-adaptive behavior of ZU-36-Ni in response to trans-C4H8 is derived from the organic linker rotation and the optimal pore dimensions, which not only improve the favorable adsorption/diffusion of trans-C4H8 with optimal host–guest interactions, but also enhance the size-exclusion of cis-C4H8. This work opens a new avenue for pore engineering in advanced smart or adaptive porous materials for specific applications involving guest molecular recognition.

Zhaoqiang Zhang;Xili Cui;Xiaoming Jiang;Qi Ding;Jiyu Cui;Yuanbin Zhang;Youssef Belmabkhout;Karim Adil;Mohamed Eddaoudi;Huabin Xing

Key Laboratory of Biomass Chemical Engineering of Ministry of Education,College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027,China;State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;Advanced Membranes and Porous Materials Center,King Abdullah University of Science and Technology,Thuwal 23955,Saudi Arabia

工程（英文）

[1]Zhaoqiang Zhang;Xili Cui;Xiaoming Jiang;Qi Ding;Jiyu Cui;Yuanbin Zhang;Youssef Belmabkhout;Karim Adil;Mohamed Eddaoudi;Huabin Xing-.Efficient Splitting of Trans-/Cis-Olefins Using an Anion-Pillared Ultramicroporous Metal–Organic Framework with Guest-Adaptive Pore Channels)[J].工程（英文）,2022(04):80-86

Olefins,Pillared,Ultramicroporous,GeFSIX

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