In this study, a novel ultramicroporous pillar-layered Ni-LAP-NH₂ [Ni₂(l-asp)₂(Pz-NH₂)] (l-asp = l-aspartic acid, Pz-NH₂ = aminopyrazine) membranes on porous α-Al₂O₃ tubes with high performance and good thermal stability was first fabricated using isostructural Ni-LAP[Ni₂(l-asp)₂(Pz)] (Pz = pyrazine) crystals as seeds. Utilizing the principle of reticular chemistry, here, we introduced the active amino side group into the Ni-LAP frameworks by replacing the pillar-layered ligand Pz with Pz -NH₂ while maintaining the original Ni-LAP small pore size, and the amino side group induced a “steric hindrance” effect and the physical adsorption affinity, which synergistically delayed CO₂ penetration. It was found that the preferential (111) orientation Ni-LAP-NH₂ membrane (Z10) exhibited a high H₂/CO₂ separation performance with a separation factor of 41.7 and H₂ permeance of 9.08 × 10^–8 mol·m^–2·s^–1·Pa^–1 under optimal conditions. These MOF materials demonstrated potential for industrial H₂ purification due to their tunable pore structure and remarkable stability. Moreover, this strategy offers an effective approach to tailoring pillar-layered MOF membranes with targeted molecular sieving ability.

中文翻译：

---

用于 H2/CO2 分离的柱状层金属-有机框架膜中的不对称孔窗


在本研究中，首次使用等结构 Ni-LAP[Ni₂（l-asp）₂ （Pz-NH₂）] 在多孔 α-Al₂O₃ 管上制备了一种新型超微孔柱层状 Ni-LAP-NH₂ [Ni₂（l-asp）₂（Pz-NH 2）]（l-asp = l-天冬氨酸，Pz-NH₂ = 氨基吡嗪）膜，具有高性能和良好的热稳定性（Pz）]（Pz = 吡嗪）晶体为种子。利用网状化学原理，在保持原有 Ni-LAP 小孔径的同时，我们用 Pz -NH₂ 取代柱层配体 Pz，将活性氨基侧基引入 Ni-LAP 框架中，氨基侧基诱导了“空间位阻”效应和物理吸附亲和力，协同延缓了 CO₂ 的渗透。结果表明，优先取向 （111） 取向 Ni-LAP-NH₂ 膜 （Z10） 表现出较高的 H₂/CO₂ 分离性能，分离因子为 41.7，H₂ 渗透率为 9.08 × 10^–8 mol·m^–2·s^–1·^Pa-1 在最佳条件下。这些 MOF 材料由于其可调的孔结构和卓越的稳定性而显示出工业 H₂ 纯化的潜力。此外，这种策略提供了一种有效的方法来定制具有靶向分子筛分能力的柱层 MOF 膜。