Lei Jiao, Yuan Wenyu, Shang Jianxuan, Xu Jie, Zhang Peng, Wang Ying, Li Yong-Peng, Zhai Quan-Guo
Key Laboratory of Macromolecular Science of Shaanxi Province, Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an, Shaanxi 710062, China.
Modern Chemical Technology Department, Shaanxi Coal and Chemical Technology Institute Co. Ltd., No. 166 Shenzhou 7th Road, Xi'an, Shaanxi 710100, China.
Inorg Chem. 2023 Sep 18;62(37):15195-15205. doi: 10.1021/acs.inorgchem.3c02347. Epub 2023 Sep 1.
Metal-organic frameworks (MOFs) have attracted extensive attention in methane (CH) purification and storage. Specially, multinuclear cluster-based MOFs usually have prominent performance because of large cluster size and abundant open metal sites. However, compared to diverse combinations of organic linkers, one MOF with two or more multinuclear clusters is difficult to achieve. In this paper, we demonstrate a mixed multinuclear cluster strategy, which successfully led to three new heterometallic MOFs (SNNU-328-330) with the same common HTATB [2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine] tritopic linker and six types of multinuclear clusters ([YCd(COO)(μ-HO)], [YCd(COO)], [In(COO)(μ-OH)], [InEu(COO)(μ-OH)(μ-O)], [Y(COO)(μ-OH)] and [YCd(COO)(μ-HO)(μ-OH)]). Three MOF adsorbents all show great potentials to remove the impurities (CO and C-hydrocarbons) in natural gas and show prominent high-pressure methane storage capacity. Among them, the ideal adsorbed solution theory separation ratios of equimolar CH/CH, CH/CH, CH/CH, and CO/CH at 298 K for SNNU-328 reach to 29.7-16.0, 19.1-8.2, 33.2-10.3, and 74.3-8.5, which have surpassed many famous MOF adsorbents. Dynamic breakthrough experiments conducted at 273 and 298 K showed that SNNU-330 can separate CH from CH/CH, CH/CH, CH/CH, and CO/CH mixtures with the breakthrough interval times of about 48.2, 17.9, 37.2, and 17.1 min g (273 K, 1 bar, / = 50/50, 2 mL min), respectively. Remarkably, SNNU-329 exhibits extremely high methane storage performance at 298 K with the total uptake and working capacity of 192 cm cm (95 bar) and 171 cm cm (65 bar) due to the synergistic effects of high surface area, suitable pore sizes, and multiple open metal sites.
金属有机框架材料（MOFs）在甲烷（CH）净化与存储方面已引起广泛关注。特别地，基于多核簇的MOFs通常因其较大的簇尺寸和丰富的开放金属位点而具有卓越性能。然而，与有机连接体的多样组合相比，具有两个或更多多核簇的单一MOF难以实现。在本文中，我们展示了一种混合多核簇策略，该策略成功制备出三种新型异金属MOFs（SNNU - 328 - 330），它们具有相同的常见HTATB [2,4,6 - 三（4 - 羧基苯基）- 1,3,5 - 三嗪]三齿连接体以及六种类型的多核簇（[YCd(COO)(μ - HO)]、[YCd(COO)]、[In(COO)(μ - OH)]、[InEu(COO)(μ - OH)(μ - O)]、[Y(COO)(μ - OH)]和[YCd(COO)(μ - HO)(μ - OH)]）。三种MOF吸附剂在去除天然气中的杂质（CO和C - 烃类）方面均展现出巨大潜力，并表现出卓越的高压甲烷存储能力。其中，SNNU - 328在298 K时等摩尔CH/CH、CH/CH、CH/CH和CO/CH的理想吸附溶液理论分离比分别达到29.7 - 16.0、19.1 - 8.2、33.2 - 10.3和74.3 - 8.5，超过了许多著名的MOF吸附剂。在273 K和298 K下进行的动态突破实验表明，SNNU - 330能够从CH/CH、CH/CH、CH/CH和CO/CH混合物中分离出CH，其突破间隔时间分别约为48.2、17.9、37.2和17.1分钟·克⁻¹（273 K，1 bar，V/F = 50/50，2 mL·分钟⁻¹）。值得注意的是，由于高比表面积、合适的孔径以及多个开放金属位点的协同效应，SNNU - 329在298 K时表现出极高的甲烷存储性能，总吸附量和工作容量分别为192 cm³·cm⁻³（95 bar）和171 cm³·cm⁻³（65 bar）。
