Selective Hysteretic Sorption of Light Hydrocarbons in a Flexible Metal-Organic Framework Material
Selective Hysteretic Sorption of Light Hydrocarbons in a Flexible Metal-Organic Framework Material
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DOI：
10.1021/acs.chemmater.6b00443
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发表时间：
2016-04-12
影响因子：
8.6
通讯作者：
Schroder, Martin
中科院分区：
文献类型：
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作者：
Gao, Shan;Morris, Christopher G.;Schroder, Martin
多孔MFM-202 a（MFM =曼彻斯特框架材料，代替NOTT名称）显示出异常高的乙炔吸收，在195 K和1.0巴下为18.3 mmol g（-1）（47.6重量%），代表迄今为止报道的框架材料的最高值。然而，在293 K和10 bar下，C2 H6吸收（9.13 mmol g（-1））是优选的。基于双位Langmuir-Freundlich（DSLF）和数值积分（NI）的LAST方法已被用于分析C1至C3烃的选择性。MFM-202 a表现出乙炔的广泛滞后解吸;这种行为对于实际气体储存是重要的，因为它允许气体在高压下被吸附，但在相对低压下储存。在MFM-202 a中还观察到其他不饱和轻质烃（乙烷和丙烯）的吸附逐步吸收和滞后释放，但不饱和烃（甲烷，乙烷和丙烷）。MFM-202 a已经通过原位同步辐射X射线粉末衍射进行了研究，以揭示作为气体负载的函数的骨架主体的可能的相变。采用LAST计算和双组分混合气体吸附实验对这些轻烃的选择性进行了综合分析，理论与实验结果吻合较好。
Porous MFM-202a (MFM = Manchester Framework Material, replacing the NOTT designation) shows an exceptionally high uptake of acetylene, 18.3 mmol g(-1) (47.6 wt %) at 195 K and 1.0 bar, representing the highest value reported to date for a framework material. However, at 293 K and 10 bar C2H6 uptake (9.13 mmol g(-1)) is preferred. Dual-site Langmuir-Freundlich (DSLF)- and Numerical Integration (NI)-based LAST methods have been used to analyze selectivities for C-1 to C-3 hydrocarbons. MFM-202a exhibits broadly hysteretic desorption of acetylene; such behavior is important for practical gas storage since it allows the gas to be adsorbed at high pressure but stored at relatively low pressure. Stepwise uptake and hysteretic release were also observed for adsorption of other unsaturated light hydrocarbons (ethane and propene) in MFM-202a but not for saturated hydrocarbons (methane, ethane, and propane). MFM-202a has been studied by in situ synchrotron X-ray powder diffraction to reveal the possible phase transition of the framework host as a function of gas loading. A comprehensive analysis for the selectivities between these light hydrocarbons has been conducted using both LAST calculation and dual-component mixed-gas adsorption experiments, and excellent agreement between theory and experiment was achieved.