Immobilization of the Polar Group into an Ultramicroporous Metal–Organic Framework Enabling Benchmark Inverse Selective CO₂/C₂H₂ Separation with Record C₂H₂ Production

One-step harvest of high-purity light hydrocarbons without the desorption process represents an advanced and highly efficient strategy for the purification of target substances. The separation and purification of acetylene (C₂H₂) from carbon dioxide (CO₂) by CO₂-selective adsorbents are urgently demanded yet are very challenging owing to their similar physicochemical properties. Here, we employ the pore chemistry strategy to adjust the pore environment by immobilizing polar groups into an ultramicroporous metal-organic framework (MOF), achieving one-step manufacture of high-purity C₂H₂ from CO₂/C₂H₂ mixtures. Embedding methyl groups into prototype stable MOF (Zn-ox-trz) not only changes the pore environment but also improves the discrimination of guest molecules. The methyl-functionalized Zn-ox-mtz thus exhibits the benchmark reverse CO₂/C₂H₂ uptake ratio of 12.6 (123.32/9.79 cm³ cm⁻³) and an exceptionally high equimolar CO₂/C₂H₂ selectivity of 1064.9 at ambient conditions. Molecular simulations reveal that the synergetic effect of pore confinement and surfaces decorated with methyl groups provides high recognition of CO₂ molecules through multiple van der Waals interactions. The column breakthrough experiments suggest that Zn-ox-mtz dramatically achieved the one-step purification capacity of C₂H₂ from the CO₂/C₂H₂ mixture with a record C₂H₂ productivity of 2091 mmol kg⁻¹, surpassing all of the CO₂-selective adsorbents reported so far. In addition, Zn-ox-mtz exhibits excellent chemical stability under different pH values of aqueous solutions (pH = 1-12). Moreover, the highly stable framework and excellent inverse selective CO₂/C₂H₂ separation performance showcase its promising application as a C₂H₂ splitter for industrial manufacture. This work paves the way to developing reverse-selective adsorbents for the challenging gas separation process.