The properties of the bonding between CO and ZIF-8 structures: a density functional theory study
The properties of the bonding between CO and ZIF-8 structures: a density functional theory study
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CO 和 ZIF-8 结构之间的键合特性：密度泛函理论研究
DOI：
10.1007/s00214-015-1636-4
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发表时间：
2015
影响因子：
1.7
通讯作者：
Wenyue Guo
中科院分区：
文献类型：
--
作者：
Haifeng Wang;Lianming Zhao;Wenbin Xu;Shengping Wang;Qiuyue Ding;Xiaoqing Lu;Wenyue Guo
利用密度泛函理论研究了具有缺陷和完整 ZIF-8 结构的 CO 分子的键合特性。通过几何参数、分子分析中的自然键轨道和原子、振动频率以及CO分子的结合能来探索它们的相互作用。结果表明，CO直接连接到完整ZIF-8结构的2-甲基咪唑配体之一上，形成C(O)·HC–C2H2N氢键。对于有缺陷的ZIF-8结构，它们分别通过C侧吸附中的强σ结合轨道和O侧吸附情况中的供体-受体相互作用形成具有弱共价性质的离子Zn-C（Zn-O）键。与完整ZIF-8结构的路易斯酸性可忽略不计相比，缺陷结构的路易斯酸性要强得多，并且其强度随着锌阳离子配位数的减少而增强。然而，发现锌阳离子接受的净电子随着配位数的减少而减少。这些定量结果将有助于了解ZIF-8中一些反应的催化机制，并促进MOFs和ZIFs金属中心的酸催化研究。
The bonding properties of CO molecule with both defective and complete ZIF-8 structures are investigated by using density functional theory. Their interaction is explored by the geometry parameters, the natural bond orbital and atoms in molecules analyses, the vibrational frequency as well as the binding energy of CO molecule. The result shows that CO attaches directly to one of the 2-methylimidazolate ligands of complete ZIF-8 structure with forming a C(O)···HC–C2H2N hydrogen bond. For defective ZIF-8 structures, they form an ionic Zn–C (Zn–O) bond with a weak covalent nature through a strong σ binding orbital in C-side adsorption and donor–acceptor interaction in O-side adsorption situation, respectively. Compared to a negligible Lewis acidity of complete ZIF-8 structure, the Lewis acidity of defective structures is much stronger, and their strengths increase with the decrease in the coordination number of zinc cation. However, the net electrons accepted by zinc cations are found to decrease with the decrease in the coordination number. These quantitative results would help to understand the catalysis mechanism of some reactions incorporated in ZIF-8 and promote the acid catalysis research with respect to metal centers of MOFs and ZIFs.
DOI：
10.1073/pnas.0602439103
发表时间：
2006-07-05
影响因子：
11.1
作者：
Park, Kyo Sung;Ni, Zheng;Yaghi, Omar M.
通讯作者：
Yaghi, Omar M.