基金属有机层通过双光激发催化演变反应
Yang Song1, Yunhong Pi1,2, Xuanyu Feng1
1Department of Chemistry, The University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, United States.
Journal of the American Chemical Society
|April 2, 2020
概括
我们合成了第一个基于的金属有机层 (MOL), Ce6-BTB, 并将其用于光催化进化. 用或复合物的修改MOL在可见光下实现了高效的生产.
科学领域:
- 材料科学
- 催化剂
- 摄影化学
背景情况:
- 基的材料如是催化过程中至关重要的.
- 金属有机层 (MOL) 为高级应用提供可调节的结构.
研究的目的:
- 合成和描述第一个基于的金属有机层 (Ce6-BTB).
- 功能化Ce6-BTB用于光催化演化反应 (HER).
- 研究功能化MOL中的光催化机制.
主要方法:
- 使用Ce6二级建筑单元 (SBU) 和BTB连接器合成Ce6-BTB.
- 用或光敏感剂对Ce6-BTB进行合成后的修饰.
- 在可见光下测量光催化演化反应 (HER).
- 用光物理和电化学研究来阐明反应机制.
主要成果:
- Ce6-BTB被成功合成并修改成Ce6-BTB-Ir和Ce6-BTB-Ru.
- 功能化的MOL显示出高效的光催化HER与高的周转率 (Ir为1357,Ru为484).
- 发现了一种涉及Ce6SBU和光敏感剂的新型双光刺激途径.
结论:
- 在可见光下,Ce6- BTB- Ir和Ce6- BTB- Ru是HER的有效光催化剂.
- 光敏剂和Ce6SBU的接近对于高效的电子传输至关重要.
- 双光激发机制增强了光催化活性.
相关概念视频
Catalysis
29.9K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
29.9K
Photochemical Electrocyclic Reactions: Stereochemistry
2.1K
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
2.1K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.8K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.8K
Reduction of Alkenes: Catalytic Hydrogenation
13.8K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
13.8K
Thermal and Photochemical Electrocyclic Reactions: Overview
2.9K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.9K
Thermal Electrocyclic Reactions: Stereochemistry
2.4K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.4K


