Incorporation of multiple supramolecular binding sites into a robust MOF for benchmark one-step ethylene purification

One-step adsorption separation of C2H4 from ternary C2 hydrocarbon mixtures remains an important and challenging goal for petrochemical industry. Current physisorbents either suffer from unsatisfied separation performance, poor stability, or are difficult to scale up. Herein, we report a strategy of constructing multiple supramolecular binding sites in a robust and scalable MOF (Al-PyDC) for highly efficient one-step C2H4 purification from ternary mixtures. Owing to suitable pore confinement with multiple supramolecular binding sites, Al-PyDC exhibits one of the highest C2H2 and C2H6 uptakes and selectivities over C2H4 at ambient conditions. The gas binding sites have been visualized by single-crystal X-ray diffraction studies, unveiling that the low-polarity pore surfaces with abundant electronegative N/O sites provide stronger multiple supramolecular interactions with C2H2 and C2H6 over C2H4. Breakthrough experiments showed that polymer-grade C2H4 can be separated from ternary mixtures with a maximum productivity of 1.61 mmol g−1. This material can be prepared from two simple reagents using a green synthesis method with water as the sole solvent, and its synthesis can be easily scaled to multikilogram batches. Al-PyDC achieves an effective combination of benchmark separation performance, high stability/recyclability, green synthesis and easy scalability to address major challenges for industrial one-step C2H4 purification.