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Published on: June 23, 2023
Adaptive Induced-Fit via Engineered Linker Regioisomerization in Biomimetic Zeolitic Imidazolate Frameworks for
Qiang Zhang1, Rajamani Krishna2, Xu Hu3
1School of Materials Science and Engineering, Academy for Advanced Interdisciplinary Studies, Nankai University, Tianjin, China.
Abstract:
Capturing and recovering sulfur hexafluoride (SF6) is a crucial yet formidable challenge in mitigating global warming. Herein, we propose a programmable linker regioisomerization strategy within zeolitic imidazolate frameworks (ZIFs) to modulate their stimulus-responsive structural flexibility, thereby significantly enhancing SF6 capture efficiency from nitrogen (N2) streams. Simultaneous regioisomerization of the methyl group in ZIF-8 and the aldehyde group in ZIF-90 on the imidazolate linkers yields ZIF-94, which exhibits a rare guest-induced reversible framework deformation upon SF6 adsorption. This behavior confers an enzyme-like induced-fit recognition mechanism for SF6 molecules, strengthening host-guest interactions. As a result, ZIF-94 achieves a high SF6 adsorption capacity of 1.97 mmol g-1 and an ultrahigh SF6 stacking density of 1438.69 mg cm-3 at 298 K and 0.1 bar, along with dramatically enhanced SF6/N2 selectivities over ZIF-8 and ZIF-90. In situ experiments and theoretical analyses reveal that the SF6-induced structural flexibility of ZIF-94 allows the framework to dynamically adjust and optimize its cage structure to match gas molecules, thus leading to significantly reinforced SF6/N2 separation performance. The experimental column breakthrough tests and pressure swing adsorption simulations confirm the practical separation performance for SF6/N2 mixtures in ZIF-94. This work offers useful insights for designing flexible adsorbents for gas separation applications.
