Propyne/propylene (C₃H₄/C₃H₆) separation is a critical process for the production of polymer‐grade C₃H₆. However, optimization of the structure of porous materials for the highly efficient removal of C₃H₄ from C₃H₆ remains challenging due to their similar structures and ultralow C₃H₄ concentration. Here, it is first reported that hybrid ultramicroporous materials with pillared inorganic anions (SiF₆²⁻ = SIFSIX, NbOF₅²⁻ = NbOFFIVE) can serve as highly selective C₃H₄ traps for the removal of trace C₃H₄ from C₃H₆. Especially, it is revealed that the pyrazine‐based ultramicroporous material with square grid structure for which the pore shape and functional site disposition can be varied in 0.1–0.5 Å scale to match both the shape and interacting sites of guest molecule is an interesting single‐molecule trap for C₃H₄ molecule. The pyrazine‐based single‐molecule trap enables extremely high C₃H₄ uptake under ultralow concentration (2.65 mmol g⁻¹ at 3000 ppm, one C₃H₄ per unit cell) and record selectivity over C₃H₆ at 298 K (>250). The single‐molecule binding mode for C₃H₄ within ultramicroporous material is validated by X‐ray diffraction experiments and modeling studies. The breakthrough experiments confirm that anion‐pillared ultramicroporous materials set new benchmarks for the removal of ultralow concentration C₃H₄ (1000 ppm on SIFSIX‐3‐Ni, and 10 000 ppm on SIFSIX‐2‐Cu‐i) from C₃H₆.

中文翻译：

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单分子丙炔捕集阱：采用阴离子填充的超微孔材料高效去除丙烯中的丙炔

丙烯/丙烯（C ₃ H ₄ / C ₃ H ₆）分离是生产聚合物级C ₃ H ₆的关键过程。然而，由于多孔材料的相似结构和超低的C ₃ H ₄浓度，优化多孔材料结构以从C ₃ H _6中高效去除C ₃ H ₄仍然具有挑战性。在这里，首次报道了具有柱状无机阴离子的混合超微孔材料（SiF ₆ ^2- = SIFSIX，NbOF ₅ ^2-= NbOFFIVE）可作为高选择性C ₃ H ₄阱，用于从C ₃ H _6中除去痕量C ₃ H ₄。特别是，揭示了具有正方形网格结构的吡嗪基超微孔材料，其孔的形状和功能位点的排列范围可以在0.1-0.5Å范围内变化，以匹配客体分子的形状和相互作用位点，这是一个有趣的单分子- C ₃ H ₄分子的分子阱。基于吡嗪的单分子阱可在超低浓度下（极高的浓度（2.65 mmol g ^-1在3000 ppm，1 C下））吸收极高的C ₃ H _4。3 H _4（每晶胞），并在298 K（> 250）下记录C ₃ H ₆上的选择性。X射线衍射实验和模型研究验证了超微孔材料中C ₃ H ₄的单分子结合模式。突破实验证实阴离子柱ultramicroporous材料用于除去超低浓度C的设置新的基准₃ ħ ₄（上SIFSIX -3-镍1000 ppm，且上SIFSIX-2-Cu系I 10 000 ppm的）选自C ₃ ħ ₆。