Scalable Green Synthesis of Robust Ultra‐Microporous Hofmann Clathrate Material with Record C3H6 Storage Density for Efficient C3H6/C3H8 Separation

Abstract Developing porous materials for C 3 H 6 /C 3 H 8 separation faces the challenge of merging excellent separation performance with high stability and easy scalability of synthesis. Herein, we report a robust Hofmann clathrate material (ZJU‐75a), featuring high‐density strong binding sites to achieve all the above requirements. ZJU‐75a adsorbs large amount of C 3 H 6 with a record high storage density of 0.818 g mL −1 , and concurrently shows high C 3 H 6 /C 3 H 8 selectivity (54.2) at 296 K and 1 bar. Single‐crystal structure analysis unveil that the high‐density binding sites in ZJU‐75a not only provide much stronger interactions with C 3 H 6 but also enable the dense packing of C 3 H 6 . Breakthrough experiments on gas mixtures afford both high separation factor of 14.7 and large C 3 H 6 uptake (2.79 mmol g −1 ). This material is highly stable and can be easily produced at kilogram‐scale using a green synthesis method, making it as a benchmark material to address major challenges for industrial C 3 H 6 /C 3 H 8 separation.