High-Connected Ternary Metal–Organic Framework Platform: Synthesis, Structure, and Methane Storage Capacity

作者：Jie Zhou, Yanan Ma, Yufeng Zhang, Bin Zheng, Ke Zheng, Shan Liu, Xin-Ai Guo, Yue‐Biao Zhang, Dong‐Xu Xue · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c04567 · 被引用次数：23 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Covalent Organic Framework Applications、Zeolite Catalysis and Synthesis

Design and synthesis of a single metal–organic framework (MOF) that simultaneously achieves high gravimetric and volumetric working capacities for methane storage are crucial for advancing the use of natural gas as a vehicular fuel. However, this presents a significant challenge due to the inherent trade-off effect between the gravimetric and volumetric methane adsorption capacities of a single porous material. Herein, we initially synthesized a novel pyridine-carboxylic acid ligand and combined it with a trimeric iron cluster along with a series of dicarboxylic acid ligands of varying lengths or functionalities. Employing a dual-solvent system and dual-modulator solvothermal principles, we successfully constructed a 9-c ternary MOF platform. X-ray diffraction analysis reveals that the structures all feature an ncb -type topological network with a cage-channel biporous hierarchy. Through a multistep solvent exchange followed by supercritical carbon dioxide drying method, we successfully activated this series of materials, achieving substantial porosity, with pore volumes exceeding 1.90 cm 3 g –1, gravimetric surface areas surpassing 4800 m 2 g –1, and volumetric surface areas greater than 1600 m 2 cm –3 . High-pressure methane adsorption tests at 80 bar demonstrated that the series of materials exhibited a high total gravimetric and volumetric methane adsorption capacity. Notably, when the testing temperature was lowered to 273 K, these materials showed significant increases ...