Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction.
Tunable Rare Earth fcu-MOF Platform: Access to Adsorption Kinetics Driven Gas/Vapor Separations via Pore Size Contraction.
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DOI：
10.1021/ja5131403
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发表时间：
2015-04
影响因子：
15
通讯作者：
D. Xue;Y. Belmabkhout;O. Shekhah;Hao Jiang;K. Adil;Amy J. Cairns;M. Eddaoudi
中科院分区：
文献类型：
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作者：
D. Xue;Y. Belmabkhout;O. Shekhah;Hao Jiang;K. Adil;Amy J. Cairns;M. Eddaoudi
采用网状化学方法成功地构建了具有限制孔径的稀土(RE，即Eu(3+), Tb（3+）和Y(3+)) fcu金属有机骨架（mof）。控制和选择性进入所产生的收缩的fcu-MOF孔允许实现必要的山梨酸切断，这是基于选择性吸附动力学的分离和/或气体和蒸汽的分子筛分的理想选择。在预先确定的反应条件下，允许原位形成12连接的RE六核分子构建块（MBB），并建立了第一个RE-fcu- mof平台，特别是在2-氟苯甲酸（2-FBA）作为调节剂和结构导向剂的情况下，基于相对较大的2连接桥接配体，即1,4-萘二羧酸酯（1,4- ndc），合成了同结构的RE-1,4- ndc -fcu- mof。随后re -1,4- ndc -fcu- mof的结构特征、收缩的窗口/孔隙和高浓度的开放金属位点，以及出色的水热稳定性和化学稳定性，产生了显著的气体/溶剂分离性能，主要是由吸附动力学驱动的，例如本研究中对正丁烷/甲烷、丁醇/甲醇和丁醇/水对体系的吸附动力学。
Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e., Eu(3+), Tb(3+), and Y(3+)) fcu metal-organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cutoff, ideal for selective adsorption kinetics based separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the first RE-fcu-MOF platform, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded notable gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol, and butanol/water pair systems.