Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units.
Extraordinary Separation of Acetylene-Containing Mixtures with Microporous Metal-Organic Frameworks with Open O Donor Sites and Tunable Robustness through Control of the Helical Chain Secondary Building Units.
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DOI：
10.1002/chem.201505107
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发表时间：
2016-04
期刊：
影响因子：
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通讯作者：
Zizhu Yao;Zhangjing Zhang;Lizhen Liu;Ziyin Li;Wei Zhou;Yunfeng Zhao;Yu Han;Banglin Chen;R. Kr
中科院分区：
文献类型：
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作者：
Zizhu Yao;Zhangjing Zhang;Lizhen Liu;Ziyin Li;Wei Zhou;Yunfeng Zhao;Yu Han;Banglin Chen;R. Kr
乙炔的分离是一个非常重要但具有挑战性的工业分离任务。通过CuI和5-三唑烟酸在不同溶剂中的溶剂热反应，得到了两种具有开放O供体位点和可控稳定性的金属有机骨架（FJU-21和FJU-22），用于乙炔的分离。它们包含相同的桨轮{Cu2（COO2）4}节点和金属配体连接模式，但具有不同的螺旋链作为二级构建单元（SBU），导致MOF的不同结构鲁棒性。FJU-21和FJU-22是第一个通过调整螺旋链SBU来控制MOF鲁棒性的例子。良好的鲁棒性使活化的FJU-22 a具有比柔性FJU-21 a更高的表面积和气体吸收。重要的是，FJU-22 a在环境条件下显示出非凡的乙炔混合物分离。FJU-22 a对50：50 C2H2/CO2混合气体的分离容量约为高容量霍夫-3的2倍，其对含1%乙炔的C2H2/C2H4混合气体的实际分离选择性在已报道的多孔材料中最高。基于第一性原理计算，FJU-22 a对C2H2的优异分离性能归因于C2H2分子与壁面上的开放O供体之间的氢键相互作用，这提供了比其他功能位点（包括开放金属位点和氨基）更好的C2H2识别能力。
Acetylene separation is a very important but challenging industrial separation task. Here, through the solvothermal reaction of CuI and 5-triazole isophthalic acid in different solvents, two metal-organic frameworks (MOFs, FJU-21 and FJU-22) with open O donor sites and controllable robustness have been obtained for acetylene separation. They contain the same paddle-wheel {Cu2(COO2)4} nodes and metal-ligand connection modes, but with different helical chains as secondary building units (SBUs), leading to different structural robustness for the MOFs. FJU-21 and FJU-22 are the first examples in which the MOFs' robustness is controlled by adjusting the helical chain SBUs. Good robustness gives the activated FJU-22 a, which has higher surface area and gas uptakes than the flexible FJU-21 a. Importantly, FJU-22 a shows extraordinary separation of acetylene mixtures under ambient conditions. The separation capacity of FJU-22 a for 50:50 C2H2/CO2 mixtures is about twice that of the high-capacity HOF-3, and its actual separation selectivity for C2H2/C2H4 mixtures containing 1% acetylene is the highest among reported porous materials. Based on first-principles calculations, the extraordinary separation performance of C2H2 for FJU-22 a was attributed to hydrogen-bonding interactions between the C2H2 molecules with the open O donors on the wall, which provide better recognition ability for C2H2 than other functional sites, including open metal sites and amino groups.