Wang Wei, Chen Yichong, Bu Xianhui, Feng Pingyun
Department of Chemistry, University of California, Riverside, California 92521, United States.
Department of Chemistry and Biochemistry, California State University, Long Beach, California 90840, United States.
J Am Chem Soc. 2025 May 7;147(18):15146-15156. doi: 10.1021/jacs.4c18251. Epub 2025 Apr 26.
From spinel gemstone (MgAlO) to layered double hydroxides, nature has long relied on combinations between charge-complementary metal ions such as divalent metal ions (M) and Al to create diverse valuable materials. However, for metal-organic frameworks (MOFs), heterometallic combinations such as Mg-Al are conspicuously absent. Here, we report a breakthrough in the synthesis of heterometallic Al-MOFs containing M/Al trimeric clusters (M = Mg, Mn, Co, Ni). The synergistic effect between M(II) chlorides and aluminum lactate plays a critical role in the cooperative crystallization of M and Al into pore-space-partitioned MOFs (partitioned acs topology) with fast crystallization kinetics (about 3 h). New M/Al MOFs exhibit highly tunable porosity and extraordinarily high uptakes for CO and small hydrocarbon molecules (112 cm/g for CO, 176 cm/g for CH, 156 cm/g for CH, and 163 cm/g for CH) at 298 K and 1 bar. The high uptake capacity coupled with high selectivity (up to 8.5 for CH/CO, 10.8 for CH/CH) gives rise to efficient separations of either CH/CO or CH/CH gas mixtures, as confirmed by experimental breakthrough experiments.
从尖晶石宝石（MgAlO）到层状双氢氧化物，长期以来大自然一直依赖于电荷互补的金属离子（如二价金属离子（M））与铝之间的组合来创造各种有价值的材料。然而，对于金属有机框架（MOF）而言，诸如Mg-Al之类的异金属组合却明显缺失。在此，我们报道了含M/Al三聚体簇（M = Mg、Mn、Co、Ni）的异金属Al-MOF合成方面的一项突破。氯化M（II）与乳酸铝之间的协同效应在M和Al协同结晶形成具有快速结晶动力学（约3小时）的孔空间分隔MOF（分隔的acs拓扑结构）过程中起着关键作用。新型M/Al MOF在298 K和1巴条件下表现出高度可调的孔隙率以及对CO和小分子烃类极高的吸附量（CO为112 cm/g，CH为176 cm/g，CH为156 cm/g，CH为163 cm/g）。通过实验突破实验证实，高吸附容量与高选择性（CH/CO高达8.5，CH/CH高达10.8）使得能够高效分离CH/CO或CH/CH气体混合物。
