Construction of Highly Porous and Robust Hydrogen‐Bonded Organic Framework for High‐Capacity Clean Energy Gas Storage

Abstract Development of highly porous and robust hydrogen‐bonded organic frameworks (HOFs) for high‐pressure methane and hydrogen storage remains a grand challenge due to the fragile nature of hydrogen bonds. Herein, we report a strategy of constructing the double‐walled framework to target highly porous and robust HOF (ZJU‐HOF‐5a) for extraordinary CH 4 and H 2 storage. ZJU‐HOF‐5a features a minimized twofold interpenetration with double‐walled structure, in which multiple supramolecular interactions are existed between the interpenetrated walls. This structural configuration can notably enhance the framework robustness while maintaining its high porosity, affording one of the highest gravimetric and volumetric surface areas of 3102 m 2 g −1 and 1976 m 2 cm −3 among the reported HOFs so far. ZJU‐HOF‐5a thus exhibits an extremely high volumetric H 2 uptake of 43.6 g L −1 at 77 K/100 bar and working capacity of 41.3 g L −1 under combined swing conditions (77 K/100 bar→160 K/5 bar), and also impressive methane storage performance with a 5–100 bar working capacity of 187 (or 159) cm 3 (STP) cm −3 at 270 K (or 296 K), outperforming most of the reported porous organic materials. Single‐crystal X‐ray diffraction studies on CH 4 ‐loaded ZJU‐HOF‐5a reveal that abundant supramolecular binding sites combined with ultrahigh porosities account for its high CH 4 storage capacities. Combined with high stability, super‐hydrophobicity, and easy recovery, ZJU‐HOF‐5a is placed among the most promising materials for H 2 and CH 4 storage applications.