Lin Xiang, Blake Alexander J, Wilson Claire, Sun Xue Zhong, Champness Neil R, George Michael W, Hubberstey Peter, Mokaya Robert, Schröder Martin
School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom.
J Am Chem Soc. 2006 Aug 23;128(33):10745-53. doi: 10.1021/ja060946u.
The robust metal-organic framework compound {[Zn(2)(L)] x 4H(2)O}(infinity) I has been synthesized by hydrothermal reaction of ZnCl(2) and 4,4'-bipyridine-2,6,2',6'-tetracarboxylic acid (H(4)L). 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) (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 (betaE(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.
通过氯化锌与4,4'-联吡啶-2,6,2',6'-四羧酸(H₄L)的水热反应合成了坚固的金属有机骨架化合物{[Zn₂(L)]×4H₂O}∞ I。化合物I结晶于手性空间群P4₂2₁2,其手性由氢键连接的客体水分子的螺旋链产生,而非配位骨架。从晶体中除去客体水分子得到多孔材料[Zn₂(L)]∞ (II),它具有非常高的热稳定性且化学惰性。II在77 K时的N₂等温线表明其具有均匀的多孔结构,BET表面积为312.7 m²/g,并且与N₂分子有非常强的相互作用(βE₀ = 29.6 kJ mol⁻¹)。II在4 bar和77 K下对H₂的储气容量为1.08 wt%,在298 K、9 Bar下对甲烷的储气容量为3.14 wt%(44.0 cm³/g,67 v/v)。还研究了II对有机溶剂蒸气的吸附行为,等温线表明对于不同的溶剂蒸气,吸附主要由两种类型的过程主导,即吸附质-吸附质或吸附质-吸附剂相互作用。II中的吸附和解吸动力学过程主要由客体物种的分子大小及其与主体的相互作用决定。