Zhou Jie, Ma Ya-Nan, Zhang Yu-Feng, Zheng Bin, Zheng Ke, Liu Shan, Guo Xin-Ai, Zhang Yue-Biao, Xue Dong-Xu
Shaanxi Key Laboratory of New Concept Sensors and Molecular Materials, Key Laboratory of Applied Surface and Colloid Chemistry of Ministry of Education, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.
College of Chemical Engineering and Technology, Taiyuan University of Science and Technology, Taiyuan 030012, China.
J Am Chem Soc. 2025 Jun 25;147(25):21811-21817. doi: 10.1021/jacs.5c04567. Epub 2025 Jun 10.
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 -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 g, gravimetric surface areas surpassing 4800 m g, and volumetric surface areas greater than 1600 m cm. 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 in total gravimetric and volumetric methane adsorption. Particularly, the Fe--TPDC-II constructed using the longest dicarboxylate linker achieved gravimetric and volumetric methane storage working capacities of 0.533 g g and 232 cm (STP) cm, respectively, performing exceptionally well compared to reported porous materials under similar conditions.
设计并合成一种单一的金属有机框架（MOF），使其同时实现用于甲烷储存的高重量和高体积工作容量，对于推动将天然气用作车辆燃料至关重要。然而，由于单一多孔材料的重量和体积甲烷吸附容量之间存在固有的权衡效应，这带来了重大挑战。在此，我们首先合成了一种新型吡啶羧酸配体，并将其与三聚体铁簇以及一系列不同长度或功能的二羧酸配体相结合。采用双溶剂体系和双调节剂溶剂热原理，我们成功构建了一个9-c三元MOF平台。X射线衍射分析表明，这些结构均具有笼-通道双孔层次结构的 - 型拓扑网络。通过多步溶剂交换，随后采用超临界二氧化碳干燥方法，我们成功激活了这一系列材料，实现了显著的孔隙率，孔体积超过1.90 cm g，重量比表面积超过4800 m g，体积比表面积大于1600 m cm。在80 bar下的高压甲烷吸附测试表明，该系列材料表现出高的总重量和体积甲烷吸附容量。值得注意的是，当测试温度降至273 K时，这些材料的总重量和体积甲烷吸附量显著增加。特别是，使用最长二羧酸连接体构建的Fe--TPDC-II分别实现了0.533 g g和232 cm（STP）cm的重量和体积甲烷储存工作容量，在类似条件下与已报道的多孔材料相比表现出色。
