Charge-Polarized Coordination Space for H2 Adsorption
Charge-Polarized Coordination Space for H2 Adsorption
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DOI：
10.1021/cm802566z
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发表时间：
2009-04
影响因子：
8.6
通讯作者：
J. Hasegawa;Masakazu Higuchi;Y. Hijikata;S. Kitagawa
中科院分区：
文献类型：
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作者：
J. Hasegawa;Masakazu Higuchi;Y. Hijikata;S. Kitagawa
我们研究了多孔配位聚合物中“电荷极化配位空间”的概念，以增加 H2 的吸附。进行从头计算来研究有机配体的 H2 吸附能力。与具有柱层结构的配位聚合物相关的吡嗪-羧酸盐配体（2.4 kcal/mol）的吸附能比单独通过范德华相互作用获得的吸附能更大。从头算能量分解分析表明，稳定性主要来自于 H2 的电子极化。因此，我们提出了“电荷极化空间”的概念来促进极化。在理想电荷极化空间产生的偶极电场下，吸附能显着增加至5−8 kcal/mol，处于存储材料中H2吸附的理想能量范围。电荷中性配体还可以提供静电极化空间。尽管结合能降低至 2 kcal/mol 左右，但 H2 聚合...
We investigated the concept “charge-polarized coordination spaces” in porous coordination polymers to increase the adsorption of H2. Ab initio calculations were performed to investigate the H2-adsorption capabilities of organic ligands. The adsorption energy of a pyrazine−carboxylate ligand (2.4 kcal/mol), relevant to a coordination polymer with a pillared layer structure, was found to be larger than that obtained by van der Waals interactions alone. An ab initio energy decomposition analysis showed that the stabilization arose mainly from the electronic polarization of H2. We therefore propose a concept of “charge-polarized spaces” to promote polarization. Under the dipolar electric field created by ideal charge-polarized spaces, the adsorption energy markedly increased to 5−8 kcal/mol, which is in the ideal energy range for H2 adsorption in storage materials. Charge-neutral ligands can also provide electrostatically polarized spaces. Although the binding energy decreases to around 2 kcal/mol, the H2 pol...