在金属-有机框架中对阴离子合电子跳转的微观洞察
Ashleigh T Castner1, Hao Su2, Erik Svensson Grape3
1Department of Chemistry-Ångström Laboratory, Uppsala University, Box 523, 75120 Uppsala, Sweden.
Journal of the American Chemical Society
|March 24, 2022
概括
在金属有机框架 (MOF) 中的电荷传输涉及电子跳跃和离子运动. 在Zr(dcphOH-NDI) MOF中,特定的阴离子链相互作用可以增强电荷传输,克服离子配对的限制.
科学领域:
- 材料科学
- 电化学
- 纳米技术
背景情况:
- 在金属有机框架 (MOF) 中,电子运输依赖于氧化还原活性位点之间的跳跃,加上反扩散.
- 在MOF中,明显的扩散系数 (D_app) 反映了电子跳转和离子迁移的贡献.
- 在MOF中对阴离子合电子转移的微观理解仍然有限.
研究的目的:
- 系统地研究MOF中阴离联电子转移的不同场景.
- 阐明在MOF中控制电荷扩散的微观机制.
- 了解阴离体大小和离子对应对电荷传输的影响.
主要方法:
- 用于测量电荷传输的溶剂和电解质离子的系统变化
- 在PIZOF类型的MOF中实验性确定明显的扩散系数 (D_app),Zr(dcphOH-NDI.
- 计算建模以分析阴子链相互作用和传输机制.
主要成果:
- 电荷迁移的明显扩散系数在 Zr ((dcphOH-NDI) 跨越两个数量级.
- 离子合电子传播的微观机制取决于离子大小和离子配对行为.
- 离子配对通常会阻碍电离体的传输,减缓电荷的传输.
结论:
- 在Zr ((dcphOH-NDI) 中的特定的阴离子链相互作用可以促进协同的阴离子合电子转移过程.
- 这些特异性相互作用可以克服减少阴离流和离子配对所造成的限制.
- 了解这些微观机制对于设计具有量身定制的电荷传输特性的MOF至关重要.
相关概念视频
Crystal Field Theory - Octahedral Complexes
28.1K
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...
28.1K
Valence Bond Theory
9.8K
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...
9.8K
Metal-Ligand Bonds
21.6K
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
21.6K


