Ultra-High Purity and Productivity Separation of CO₂ and C₂H₂ from CH₄ in Rigid Layered Ultramicroporous Material

Efficiently obtaining both high-purity gas-phase and adsorbed-phase products in a single physisorption process presents the challenge of simultaneously achieving high selectivity and uptake and rapid diffusion in adsorbents. With a focus on natural gas purification and high-purity acetylene production, we report for the first time that the synergistic ligand/anion binding mode and multiple diffusion pathways in a robust 2D layered ultramicroporous framework (ZUL-100) enable unprecedented carbon dioxide/methane and acetylene/methane separation performance. Taking advantage of its rich anion, functional ligand ,and rigid 3D interpenetrated ultramicroporous channels, ZUL-100 achieved record IAST selectivities for equimolar carbon dioxide/methane (3.2 × 10⁵) and acetylene/methane (1.7 × 10¹⁰) mixtures, accompanied by record dynamic uptakes of carbon dioxide (3.10 mmol/g) and acetylene (4.79 mmol/g), respectively. The strong affinity and fast mass transfer of carbon dioxide and acetylene on ZUL-100 were systematically elucidated by a combination of in situ FTIR, single-crystal XRD, kinetic tests, and DFT-D adsorption/diffusion modeling. In particular, high-purity (≥99.999%) methane and carbon dioxide (acetylene) can both be obtained on ZUL-100 through a single adsorption-desorption cycle, with exceptional productivity (2.81-4.22 mmol/g of methane, 2.96 mmol/g of carbon dioxide, and 4.31 mmol/g of acetylene) and high yield (95.5% for carbon dioxide and 90.0% for acetylene).