在霍夫曼型多孔协调聚合物中吸收CO2和CS2:静电与分散相互作用
Milind Madhusudan Deshmukh1, Masaaki Ohba, Susumu Kitagawa
1Fukui Institute for Fundamental Chemistry, Kyoto University, Takano, Kyoto 606-8103, Japan.
Journal of the American Chemical Society
|February 27, 2013
概括
这项研究表明,多孔协调聚合物强烈吸收二硫化碳 (CS2),但由于不同的相互作用,吸收二氧化碳 (CO2) 很弱,这有助于气体分离材料的设计.
科学领域:
- 材料科学 材料科学 材料科学
- 计算化学计算化学
- 物理化学 物理化学
背景情况:
- 孔隙协调聚合物 (PCP) 正在研究气体吸附应用.
- 了解PCP中的分子相互作用对于设计选择性吸附剂至关重要.
研究的目的:
- 从理论上探索二氧化碳 (CO2) 和二硫化碳 (CS2) 在霍夫曼型PCP中吸收的过程.
- 阐明控制二氧化碳和CS2的差异吸附的相互作用机制.
主要方法:
- 使用ONIOM ((MP2.5或SCS-MP2:DFT) 理论方法与M06-2X功能.
- 计算了结合能,并进行了能量分解分析 (EDA).
- 将理论预测与实验性X射线结构进行比较.
主要成果:
- CS2对PCP表现出强大的结合 (-17.3 kcal mol-1),而CO2表现出弱的结合 (-5.2 kcal mol-1).
- CS2强烈吸附的原因是显著的分散相互作用.
- 二氧化碳的弱吸附和明显的位置与静电相互作用和弱分散有关.
结论:
- 霍夫曼型的PCP {Fe(Pz) [Pt(CN) [4]}n表明选择性吸附有利于CS2而不是CO2.
- 分散力在CS2吸附中起着关键作用,而静电相互作用决定了CO2的位置.
- 结果为设计具有定制气体吸收特性的PCP提供了洞察力.
相关概念视频
Valence Bond Theory
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
Valence Bond Theory
Overview of Valence Bond Theory
Crystal Field Theory - Octahedral Complexes
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Van der Waals Interactions
Atoms and molecules interact with each other through intermolecular forces. These electrostatic forces arise from attractive or repulsive interactions between particles with permanent, partial, or temporary charges. The intermolecular forces between neutral atoms and molecules are ion–dipole, dipole–dipole, and dispersion forces, collectively known as van der Waals forces.
Intermolecular Forces
Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen bonds, and dispersion...
Molecular Shape and Polarity
Dipole Moment of a Molecule


