Porous Metal-Organic Frameworks Based on an Anthracene Derivative: Syntheses, Structure Analysis, and Hydrogen Sorption Studies
Porous Metal-Organic Frameworks Based on an Anthracene Derivative: Syntheses, Structure Analysis, and Hydrogen Sorption Studies
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DOI：
10.1021/ic900217t
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发表时间：
2009-06-15
影响因子：
4.6
通讯作者：
Zhou, Hong-Cai
中科院分区：
文献类型：
--
作者：
Ma, Shengqian;Simmons, Jason M.;Zhou, Hong-Cai
5,5'-(9,10-蒽二基)二间苯二甲酸酯(H(4)adip)与原位生成的二铜和二铁浆轮二次构建单元(SBU)的溶剂热组装提供了两种多孔金属有机框架(MOF)，分别命名为PCN-14和PCN-15。两种MOF以不同的结构结晶，其特征在于蒽和adip配体的苯环之间的二面角不同。 PCN-14 在脱水下保留永久孔隙率并包含纳米级笼，而 PCN-15 仅包含沿 (0 0 1) 方向的一维六边形通道，需要溶剂稳定。 adip 配体的蒽环的芳香性与纳米笼相结合，赋予 PCN-14 在 77 K、760 Torr（饱和时为 4.42 wt%）下 2.70 wt% 的高过量氢吸附能力，以及在低 H-2 覆盖率下 8.6 kJ/mol 的高氢亲和力。将这些值与其他四羧酸盐衍生的 MOF 进行比较，以更好地了解芳香环在氢吸附中的作用。
Solvothermal assembly of 5,5'-(9,10-anthracenediyl)di-isophthalate (H(4)adip) with in situ-generated dicopper and diiron paddlewheel secondary building units (SBUs) afforded two porous metal-organic frameworks (MOFs), designated as PCN-14 and PCN-15, respectively. The two MOFs crystallize in different structures, characterized by a difference in the dihedral angles between the anthracene and the phenyl rings of the adip ligand. PCN-14 retains permanent porosity under dehydration and contains nanoscopic cages while PCN-15 contains only one-dimensional hexagonal channels along the (0 0 1) direction which require solvent stabilization. The aromaticity of the anthracene rings of the adip ligand in conjunction with the nanoscopic cages grants PCN-14 high excess hydrogen adsorption capacity of 2.70 wt% at 77 K, 760 Torr (4.42 wt % at saturation), as well as high hydrogen affinity of 8.6 kJ/mol at low H-2 coverage. These values are compared to other tetracarboxylate-derived MOFs to better understand the role of the aromatic rings in hydrogen adsorption.