We investigated the interwoven isomerism in 3D hydrogen-bonded organic frameworks (HOFs) YSH-8_Ni and YSH-8_Zn, demonstrating their effectiveness in natural gas purification. These frameworks, constructed from 5,10,15,20-tetrakis(3,5-dicarboxyphenyl)porphyrins (TDCPP_Ms; M = Ni and Zn), exhibit 2-fold and 4-fold interwoven structures of 3D hydrogen-bonded networks. YSH-8_Ni exhibited a 4-fold interwoven structure with stabilisation of π–π interaction among porphyrin building blocks. YSH-8_Zn exhibited a 2-fold interwoven structure with axial coordination of oxygen species. Post solvent exchange to n-hexane, YSH-8_Zn/Hx exhibited improved stability through the connection by bridging ligand atoms between the 2-fold interwoven hydrogen-bonded networks. After activation, YSH-8_Zn/Hx* shows a BET surface area of 1665 m² g⁻¹, which is six times larger than that of YSH-8_Ni* (279.5 m² g⁻¹). YSH-8_Zn/Hx* exhibits outstanding selectivity for C₃H₈ over C₂H₆, C₃H₈ over CH₄, and C₂H₆ over CH₄, matching or exceeding the performance of leading benchmark materials. Dynamic breakthrough tests confirm its efficiency in separating CH₄ from C₃H₈/C₂H₆/CH₄ mixtures, C₂H₆ from C₃H₈/C₂H₆ mixtures, and CH₄ from C₂H₆/CH₄ mixtures. The stability of YSH-8_Zn/Hx* is evident from consistent breakthrough curves and PXRD patterns across three recycling cycles, underscoring its potential as a robust adsorbent for practical gas separation applications.

中文翻译：

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3D氢键有机框架中轴向配位辅助交织异构现象用于高效天然气净化


我们研究了 3D 氢键有机骨架 (HOF) YSH-8 _Ni和YSH-8 _Zn中的交织异构现象，证明了它们在天然气净化中的有效性。这些框架由 5,10,15,20-四(3,5-二羧基苯基)卟啉 (TDCPP _M s; M = Ni 和 Zn) 构建，表现出 3D 氢键网络的 2 倍和 4 倍交织结构。 YSH-8 _Ni呈现出 4 重交织结构，卟啉结构单元之间的 π-π 相互作用稳定。 YSH-8 _Zn表现出具有氧物种轴向配位的2重交织结构。溶剂交换为正己烷后， YSH-8 _Zn/Hx通过在 2 重交织的氢键网络之间桥接配体原子而表现出更高的稳定性。活化后， YSH-8 _Zn/Hx *的BET表面积为1665 m ² g ^-1 ，是YSH-8 _Ni * (279.5 m ² g ^-1 )的六倍。 YSH-8 _Zn/Hx *对 C ₃ H ₈优于 C ₂ H ₆ 、C ₃ H ₈优于 CH ₄ 、C ₂ H ₆优于 CH ₄表现出出色的选择性，匹配或超过领先基准材料的性能。动态突破测试证实了其从 C ₃ H ₈ /C ₂ H ₆ /CH ₄混合物中分离 CH ₄ 、从 C ₃ H ₈ /C ₂ H ₆混合物中分离 C ₂ H ₆以及从 C ₂ H ₆ / 中分离 CH _{4 的}效率。 CH ₄混合物。从三个回收周期中一致的突破曲线和 PXRD 图案可以看出， YSH-8 _Zn/Hx *的稳定性显而易见，强调了其作为实际气体分离应用的强大吸附剂的潜力。