High-enthalpy hydrogen adsorption in cation-exchanged variants of the microporous metal-organic framework Mn3[(Mn4Cl)3(BTT)8(CH3OH)10]2
High-enthalpy hydrogen adsorption in cation-exchanged variants of the microporous metal-organic framework Mn3[(Mn4Cl)3(BTT)8(CH3OH)10]2
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DOI：
10.1021/ja072871f
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发表时间：
2007-09-12
影响因子：
15
通讯作者：
Long, Jeffrey R.
中科院分区：
文献类型：
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作者：
Dinca, Mircea;Long, Jeffrey R.
Mn-3[（Mn_4Cl）（3）（BTT）（8）（CH_3OH）（10）]（2）（1-Mn ~（2+）; BTT = 1，3，5-benzenetristetrazolate）中的客体Mn ~（2+）与选定的阳离子交换，形成同构骨架化合物1-M（M = Li ~+，Cu ~+，Fe ~（2+），CO ~（2+），Ni ~（2+），Cu ~（2+），Zn ~（2+））。与母体化合物类似，新的微孔材料对去溶剂化稳定，并表现出高的H-2储存容量，在77 K和900 ℃下为2.00至2.29 wt %。在零覆盖率的吸附热的等排的测量揭示了最弱和最强的H-2-结合材料之间的2 kJ/mol的差异，这是由于在每个框架内的H-2分子和不饱和金属中心之间的相互作用的强度的变化。的Co 2+交换的化合物-CO2+，表现出的初始吸附焓为10.5 kJ/mol，最高的微孔金属-有机框架尚未观察到的。
Exchange of the guest Mn2+ ions in Mn-3[(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+, Fe (2+), CO2+, Ni2+, CU2+, Zn2+). Similar to the parent compound, the new microporous materials are stable to desolvation and exhibit a high H-2 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 H-2-binding materials, which is attributed to variations in the strength of interaction between H-2 molecules and unsaturated metal centers within each framework. The Co2+-exchanged compound-CO2+, exhibits an initial enthalpy of adsorption of 10.5 kJ/mol, the highest yet observed for a microporous metal-organic framework.