Dinca Mircea, Long Jeffrey R
Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Am Chem Soc. 2007 Sep 12;129(36):11172-6. doi: 10.1021/ja072871f. Epub 2007 Aug 18.
Exchange of the guest Mn2+ ions in Mn3[(Mn4Cl)3(BTT)8(CH3OH)10]2 (1-Mn2+; BTT=1,3,5-benzenetristetrazolate) with selected cations results in the formation of isostructural framework compounds 1-M (M=Li+, Cu+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+). Similar to the parent compound, the new microporous materials are stable to desolvation and exhibit a high H2 storage capacity, ranging from 2.00 to 2.29 wt % at 77 K and 900 torr. Measurements of the isosteric heat of adsorption at zero coverage reveal a difference of 2 kJ/mol between the weakest and strongest H2-binding materials, which is attributed to variations in the strength of interaction between H2 molecules and unsaturated metal centers within each framework. The Co2+-exchanged compound, 1-Co2+, exhibits an initial enthalpy of adsorption of 10.5 kJ/mol, the highest yet observed for a microporous metal-organic framework.
在Mn3[(Mn4Cl)3(BTT)8(CH3OH)10]2（1-Mn2+；BTT = 1,3,5-苯三唑）中，客体Mn2+离子与选定的阳离子进行交换，形成了同构骨架化合物1-M（M = Li+、Cu+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+）。与母体化合物类似，这些新型微孔材料对去溶剂化稳定，并且在77 K和900托下表现出2.00至2.29 wt%的高氢气储存容量。零覆盖度下吸附等量热的测量结果表明，最弱和最强的H2结合材料之间存在2 kJ/mol的差异，这归因于每个骨架内H2分子与不饱和金属中心之间相互作用强度的变化。Co2+交换的化合物1-Co2+表现出10.5 kJ/mol的初始吸附焓，这是微孔金属有机骨架中迄今观察到的最高值。
