A porous framework polymer based on a zinc(II) 4,4′-bipyridine-2,6,2′,6′-tetracarboxylate:: Synthesis, structure, and "zeolite-like" behaviors
A porous framework polymer based on a zinc(II) 4,4′-bipyridine-2,6,2′,6′-tetracarboxylate:: Synthesis, structure, and "zeolite-like" behaviors
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DOI：
10.1021/ja060946u
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发表时间：
2006-08-23
影响因子：
15
通讯作者：
Schroder, Martin
中科院分区：
文献类型：
--
作者：
Lin, Xiang;Blake, Alexander J.;Schroder, Martin
以氯化锌和4，4‘-联吡啶-2，6，2’，6‘-四羧酸(H4L)为原料，通过水热反应合成了坚固的金属-有机骨架化合物{[Zn-2(L)](.)4H(2)O}(无穷大)。化合物I在手性空间群P4(2)2(1)2中结晶，其手性是由氢键客水分子的螺旋链产生的，而不是由配位框架产生。从晶体中除去客体水分子得到了多孔材料[Zn-2(L)](无穷大)(II)，它具有非常高的热稳定性和化学惰性。77 K时II的N-2等温线表明其具有均匀的孔道结构，比表面积为312.7 m(2)/g，与N-2分子(βE-0)有很强的相互作用，为29.6kJ摩尔(-1)。在298K、4bar和77K下，II对H-2的储气量分别为1.08wt%和3.14wt%(44.0 cm(3)/g、67v/v)，对甲烷的储气量为3.14wt%(44.0 cm(3)/g、67v/v)。吸附和解吸动力学过程主要由客体物种的分子尺寸及其与宿主的相互作用决定。
The robust metal-organic framework compound {[Zn-2(L)](.)4H(2)O}(infinity) I has been synthesized by hydrothermal reaction of ZnCl2 and 4,4 '-bipyridine-2,6,2 ',6 '-tetracarboxylic acid (H4L). Compound I crystallizes in a chiral space group, P4(2)2(1)2, with the chirality generated by the helical chains of hydrogen-bonded guest water molecules rather than by the coordination framework. Removal of guest water molecules from the crystal affords the porous material, [Zn-2(L)](infinity) (II), which has very high thermal stability and is chemically inert. The N-2 isotherm of II at 77 K suggests a uniform porous structure with a BET surface area of 312.7 m(2)/g and a remarkably strong interaction with N-2 molecules (beta E-0) 29.6 kJ mol(-1). II also exhibits significant gas storage capacities of 1.08 wt % for H-2 at 4 bar and 77 K and 3.14 wt % (44.0 cm(3)/g, 67 v/v) for methane at 9 Bar at 298 K. The adsorption behavior of II toward organic solvent vapors has also been studied, and isotherms reveal that for different solvent vapors adsorption is dominated by two types of processes, absorbate-absorbate or absorbate-absorbent interactions. The adsorption and desorption kinetic processes in II are determined mainly by the molecular size of the guest species and their interaction with the host.