Acetylene (C₂H₂) and carbon dioxide (CO₂) both are linear molecules and the similarity in size and physical properties makes their separation very challenging. Compared to the C₂H₂-selective C₂H₂/CO₂ separation, the inscrutable CO₂-selective capture (also called inverse C₂H₂/CO₂ separation) process is ideal as it enables one-step production of high-purity C₂H₂. Herein, we demonstrate the controllable C₂H₂/CO₂ inverse adsorption and separation in a series of isomorphic Zn-1,2,4-triazolate-dicarboxylate pillar-layered frameworks (Zn-FA-TRZ, Zn-MUC-TRZ, and Zn-BDC-TRZ) based on the aromaticity modulation strategy. Compared with Zn-MUC-TRZ, the utilization of shorter FA linker only with one double bond leads to an intersection point between the isothermal adsorption curves. After the intersection points, Zn-FA-TRZ showed higher CO₂ uptakes than C₂H₂ (thermodynamic inversion) and the intersection point moving towards the high-pressure region with the increasing temperature. When BDC involved, the enhanced ligand aromaticity enables a complete thermodynamic inversion for C₂H₂ and CO₂ adsorption due to the much stronger interactions between the aromatic ring and CO₂ molecules. The isosteric heats of adsorption for CO₂ and C₂H₂ clearly support such inverse adsorption induced by the ligand aromaticity. Furthermore, the fixed-bed dynamic breakthrough experiments indicate that Zn-FA-TRZ and Zn-MUC-TRZ both have common C₂H₂-selective separation process, but Zn-BDC-TRZ adsorbent shows a prominent CO₂-selective inverse C₂H₂/CO₂ separation. Specially, with temperature increased, the inverse separation performance enhanced, and high purity C₂H₂ (>99.99 %) can be obtained via one-step separation from C₂H₂/CO₂ (50/50) mixture at room temperature. Overall, inverse C₂H₂/CO₂ separation was successfully achieved in pillar-layered metal–organic frameworks, which is helpful for the exploration of practical acetylene adsorbents.

乙炔（C ₂ H ₂ ）和二氧化碳（CO ₂）都是线性分子，尺寸和物理性质的相似性使得它们的分离非常具有挑战性。与C ₂ H ₂选择性C ₂ H ₂ /CO ₂分离相比，难以理解的CO ₂选择性捕获（也称为逆C ₂ H ₂ /CO ₂分离）过程是理想的，因为它可以一步生产高浓度的CO 2 H 2 。 -纯度C ₂ H ₂。在此，我们演示了可控的C ₂ H ₂ /CO ₂基于芳香度调节策略的一系列同构 Zn-1,2,4-三唑酯-二羧酸盐柱状层状框架（Zn-FA-TRZ、Zn-MUC-TRZ 和 Zn-BDC-TRZ）的逆吸附和分离。与 Zn-MUC-TRZ 相比，使用仅具有一个双键的较短 FA 连接体会导致等温吸附曲线之间出现交点。在交点之后，Zn-FA-TRZ表现出比C ₂ H _{2 (热力学反转)更高的CO 2}吸收，并且交点随着温度的升高向高压区移动。_{当 BDC 参与时，增强的配体芳香性能够实现 C 2} H ₂和 CO ₂的完全热力学反转_{由于芳环和CO 2}分子之间更强的相互作用而产生吸附。_{CO 2}和C ₂ H ₂的等量吸附热清楚地支持由配体芳香性诱导的这种逆吸附。此外，固定床动态突破实验表明，Zn-FA-TRZ和Zn-MUC-TRZ都具有共同的C ₂ H ₂选择性分离过程，但Zn-BDC-TRZ吸附剂表现出突出的CO ₂选择性逆C ₂ H ₂ /CO ₂分离。特别是，随着温度升高，逆分离性能增强，C ₂ H纯度高₂ (>99.99%)可以通过在室温下从C ₂ H ₂ /CO ₂ (50/50)混合物中一步分离得到。总体而言，在柱状层状金属有机框架中成功实现了C ₂ H ₂ /CO _{2的逆分离，这有助于探索实用的乙炔吸附剂。}