Enhanced Gas Uptake in a Microporous Metal-Organic Framework via a Sorbate Induced-Fit Mechanism.
Enhanced Gas Uptake in a Microporous Metal-Organic Framework via a Sorbate Induced-Fit Mechanism.
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通过山梨酸盐诱导配合机制增强微孔金属有机框架中的气体吸收
DOI：
10.1021/jacs.9b07807
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发表时间：
2019-11-06
影响因子：
15
通讯作者：
Bu XH
中科院分区：
文献类型：
--
作者：
Yu MH;Space B;Franz D;Zhou W;He C;Li L;Krishna R;Chang Z;Li W;Hu TL;Bu XH
气体分子在微孔材料中的物理吸附是一个放热过程，解吸熵随温度降低。在多孔材料中，随着温度的升高而增强的气体吸附是罕见的，并且指示吸附物引发的结构变化。在此，沿着其它小分子和烃吸附等温线一起报道了C2 H6、C3 H6和C3 H8在柔性微孔金属有机骨架（MOF）{Cu-（FPBDC）]·DMF}n（NKU-FlexMOF-1）（H2 FPBDC = 5-（5-氟吡啶-3-基）-1，3-苯二甲酸）中的吸附，其在实际有用的温度和压力范围内随温度升高而增加。单X射线衍射研究，温度依赖的气体吸附等温线，在原位和变温粉末X射线衍射实验，和电子结构计算进行表征的构象依赖的吸附行为在NKU-FlexMOF-1。总之，数据支持非典型吸附行为是由山梨酸酯特异性客体-骨架相互作用诱导的NKU-FlexMOF-1柔性骨架中的负载依赖性结构变化的结果。山梨酸盐引起与每种山梨酸盐不同的框架的微妙适应，提供诱导配合分离机制以通过高度特异性的山梨酸盐-吸附剂相互作用来解析化学上相似的烃。相关的分子间接触被证明是主要的排斥和分散的相互作用。还发现NKU-FlexM 0 F-1在水溶液中是稳定的，包括耐受pH变化。这些实验证明了这种柔性微孔MOF用于成本和能量有效的工业烃分离和纯化工艺的潜力。使用NKU-FlexMOF-1a（即，活化的NKU-FlexMOF-1）。
Physical adsorption of gas molecules in microporous materials is an exothermic process, with desorption entropy driving a decrease in uptake with temperature. Enhanced gas sorption with increasing temperature is rare in porous materials and is indicative of sorbate initiated structural change. Here, sorption of C2H6, C3H6, and C3H8 in a flexible microporous metal–organic framework (MOF) {Cu-(FPBDC)]·DMF}n (NKU-FlexMOF-1) (H2FPBDC = 5-(5-fluoropyridin-3-yl)-1,3-benzenedicarboxylic acid) that increases with rising temperature over a practically useful temperature and pressure range is reported along with other small molecule and hydrocarbon sorption isotherms. Single X-ray diffraction studies, temperature-dependent gas sorption isotherms, in situ and variable temperature powder X-ray diffraction experiments, and electronic structure calculations were performed to characterize the conformation-dependent sorption behavior in NKU-FlexMOF-1. In total, the data supports that the atypical sorption behavior is a result of loading-dependent structural changes in the flexible framework of NKU-FlexMOF-1 induced by sorbate-specific guest–framework interactions. The sorbates cause subtle adaptations of the framework distinct to each sorbate providing an induced-fit separation mechanism to resolve chemically similar hydrocarbons through highly specific sorbate–sorbent interactions. The relevant intermolecular contacts are shown to be predominantly repulsion and dispersion interactions. NKU-FlexMOF-1 is also found to be stable in aqueous solutions including toleration of pH changes. These experiments demonstrate the potential of this flexible microporous MOF for cost and energy efficient industrial hydrocarbon separation and purification processes. The efficacy for the separation of C3H6/C3H8 mixtures is explicitly demonstrated using NKU-FlexMOF-1a (i.e., activated NKU-FlexMOF-1) for a particular useful temperature range.
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影响因子：
29.4
作者：
Chang, Ze;Yang, Dong-Hui;Bu, Xian-He
通讯作者：
Bu, Xian-He
影响因子：
15
作者：
Le Ouay, Benjamin;Kitagawa, Susumu;Uemura, Takashi
通讯作者：
Uemura, Takashi
影响因子：
56.9
作者：
Cadiau, A.;Adil, K.;Eddaoudi, M.
通讯作者：
Eddaoudi, M.
影响因子：
64.8
作者：
Mason, Jarad A.;Oktawiec, Julia;Long, Jeffrey R.
通讯作者：
Long, Jeffrey R.
用于从丙烯中高效去除丙炔的柔性-鲁棒金属有机框架
影响因子：
15
作者：
Li, Libo;Lin, Rui-Biao;Chen, Banglin
通讯作者：
Chen, Banglin