Development of a Mixed Multinuclear Cluster Strategy in Metal–Organic Frameworks for Methane Purification and Storage

作者：Jiao Lei, Wenyu Yuan, Jianxuan Shang, Jie Xu, Peng Zhang, Ying Wang, Yongpeng Li, Quan‐Guo Zhai · 发表于：Inorganic Chemistry · 年份：2023 · DOI：10.1021/acs.inorgchem.3c02347 · 被引用次数：26 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Covalent Organic Framework Applications、Lanthanide and Transition Metal Complexes

Metal–organic frameworks (MOFs) have attracted extensive attention in methane (CH 4 ) 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 H 3 TATB [2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine] tritopic linker and six types of multinuclear clusters ([YCd(COO) 4 (μ 2 -H 2 O)], [YCd 2 (COO) 8 ], [In 3 (COO) 6 (μ 3 -OH)], [In 3 Eu 2 (COO) 9 (μ 3 -OH) 3 (μ 4 -O)], [Y 9 (COO) 12 (μ 3 -OH) 14 ] and [Y 2 Cd 8 (COO) 16 (μ 2 -H 2 O) 4 (μ 3 -OH) 8 ]). Three MOF adsorbents all show great potentials to remove the impurities (CO 2 and C 2 -hydrocarbons) in natural gas and show prominent high-pressure methane storage capacity. Among them, the ideal adsorbed solution theory separation ratios of equimolar C 2 H 2 /CH 4, C 2 H 4 /CH 4, C 2 H 6 /CH 4, and CO 2 /CH 4 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 4 from C 2 H 2 /CH 4, C 2 H 4 /CH 4, C 2 H 6 /CH 4, and CO 2 /CH 4 mixtures with the breakthrough interval times...