Controllable C2H2/CO2 inverse adsorption and separation in pillar-layered Zn-1,2,4-triazolate-dicarboxylate frameworks induced by the ligand aromaticity

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.