通过金属-有机框架中的Exciplex类复杂构成促进的小型驱动力的光诱导电荷转移
Xinlin Li1, Jierui Yu1, Zhiyong Lu2,3
1School of Chemical and Biomolecular Science, Southern Illinois University, 1245 Lincoln Drive, Carbondale, Illinois 62901, United States.
Journal of the American Chemical Society
|September 9, 2021
概括
这项研究引入了基于金属有机框架 (MOF) 的新型光采集系统,使用定制的色素. 这些系统实现了高效的光诱导电荷转移,而能量损耗很小,为先进的能量转换技术铺平了道路.
科学领域:
- 材料科学
- 摄影化学
- 纳米技术
背景情况:
- 光诱导电荷转移 (PCT) 对于光采集 (LH) 能量转换至关重要.
- 由于PCT的高驱动力,现有的LH系统往往有很大的能量损失.
- 模仿自然光采集复合物需要在染色体内有效的PCT.
研究的目的:
- 设计和合成MOF衍生的LH系统,尽量减少PCT的能量损失.
- 模仿天然LH反应中心的电荷载体生成效率.
- 调整MOF毛孔内的最佳PCT的氧化还原潜力.
主要方法:
- 通过溶剂辅助合物 (SALI) 将电子多样化的甲 (BFBP(Zn) -COOH,TFP ((Zn) -COOH) 纳入NU-1000 MOF.
- 通过变化的三甲基替代调整氨酸的氧化还原潜力.
- 使用时间分辨率光谱来研究能量转移 (EnT) 和电荷分离动态.
主要成果:
- 成功合成了BFBP(Zn) @NU-1000和TFP(Zn) @NU-1000可调节的氧化还原潜力和PCT的小 ΔG0.
- 观察到不同的能量传输路径:在BFBP (Zn) @NU-1000中缓慢的中间形成和在TFP (Zn) @NU-1000中高效的EnT到预先形成的基态复合物.
- 证明形成具有高潜力的长寿命电荷分离状态.
结论:
- 在MOF中开发合成LH系统,以尽量减少PCT期间的能量损失.
- 通过分子设计建立了控制PCT通路和充电载体潜力的方法.
- 结果为能源转换应用提供了高效合成光采集系统的途径.
更多相关视频
06:53Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
2.2K
05:47Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
7.9K
相关概念视频
02:58Crystal Field Theory - Octahedral Complexes
28.5K
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...
28.5K
00:56Extraction: Advanced Methods
605
Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
605
02:51Metal-Ligand Bonds
22.3K
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...
22.3K
01:26Photochemical Electrocyclic Reactions: Stereochemistry
2.0K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
2.0K