Ligand Torsion Triggered Two Robust Fe-Tetratopic Carboxylate Frameworks with Enhanced Gas Uptake and Separation Performance
Ligand Torsion Triggered Two Robust Fe-Tetratopic Carboxylate Frameworks with Enhanced Gas Uptake and Separation Performance
复制标题
配体扭转触发了两种具有增强气体吸收和分离性能的鲁棒铁四位羧酸盐框架
DOI：
10.1002/chem.201700867
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发表时间：
2017
影响因子：
4.3
通讯作者：
Zhai Quan-Guo
中科院分区：
文献类型：
--
作者：
Zhang Jian-Wei;Hu Man-Cheng;Li Shu-Ni;Jiang Yu-Cheng;Zhai Quan-Guo
通过调节四配位羧酸盐配体，两种稳健的Fe-MOFs在DMA/DMSO/HBF 4溶剂体系下包含三角棱柱结构单元的金属-有机骨架，即[（CH 3）2NH 2][FeII 3（OH）（BPTC）1.5（DMSO）3]（SNNU-60）和[FeIIIFeII 2（OH）（ABTC）1.5（DMSO）3]（SNNU-61）（BPTC= 3，3 ′，5，5 ′-联苯四甲酸，ABTC= 3，3 ′，5，5 ′-偶氮苯四甲酸，SNNU=陕西师范大学）。配体的苯环之间的扭转导致两种MOF表现出完全不同的（4，6）连接框架，这代表了迄今为止仅有的两种由[M3（O/OH）（COO）6]三聚体构建单元和四边形四位羧酸酯连接体构建的MOF类型。坚固的Fe-MOFsSNNU-60和SNNU-61均表现出高的热/化学稳定性、永久性微孔性以及在1 bar下对H2、CO2、C2 H2和C2 H4的优异气体吸收能力。SNNU-60尤其在低压下表现出非常高的C2 H2捕获能力（在0.15 bar和298 K下为85 cm 3cm − 3），这是顶级的C2 H2吸收MOF材料之一。 此外，这两种Fe-MOF显示出相对于CH 4的CO2和C2-烃的高分离。值得注意的是，由于高稳定性，合适的孔径，开放的Fe位点和离子骨架，SNNU-60具有极高的C2 H2/CH 4选择性（83.6，298 K），这超过了迄今为止在相同条件下报道的大多数MOFs。
By regulating the tetratopic carboxylate ligands, two robust Fe‐MOFs (MOF=Metal‐organic framework) comprising trigonal prismatic building blocks under a DMA/DMSO/HBF4solvent system, namely, [(CH3)2NH2][FeII3(OH)(BPTC)1.5(DMSO)3] (SNNU‐60) and [FeIIIFeII2(OH)(ABTC)1.5(DMSO)3] (SNNU‐61) (BPTC=3,3′,5,5′‐biphenyltetracarboxylic acid, ABTC=3,3′,5,5′‐azobenzenetetracarboxylic acid, SNNU=Shaanxi Normal University) have been successfully synthesized. The torsions between the benzene groups of the ligands result in two MOFs exhibiting completely different (4,6)‐connected frameworks, which represent the only two MOF types constructed by [M3(O/OH)(COO)6] trimeric building units and quadrilateral tetratopic carboxylate linkers until now. The robust Fe‐MOFsSNNU‐60andSNNU‐61both exhibit high thermal/chemical stability, permanent microporosity, and excellent gas uptake capability for H2, CO2, C2H2, and C2H4under 1 bar.SNNU‐60in particular displays very high C2H2capture under low pressure (85 cm3cm−3at 0.15 bar and 298 K), which is among the top C2H2uptake MOF materials. Also, these two Fe‐MOFs display high separation for CO2and C2‐hydrocarbons over CH4. Significantly, thanks to the high stability, suitable pore size, open Fe sites, and ion skeleton,SNNU‐60has extremely high C2H2/CH4selectivity (83.6, 298 K), which surpasses most MOFs reported so far under the same conditions.