可见光可切换格子氧气位点用于选择性C-H和C-O-C键电氧化
Keping Wang1, Jinshu Huang1, Jinguang Hu2
1State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, Guiyang, 550025, China.
Angewandte Chemie (International ed. in English)
|September 9, 2024
概括
可见光使一种新的氧化催化剂 (ESE-NiOOH) 能够在废物中裂解C-O-C键. 这个过程有效地将木质素和塑料转化为有价值的酸,提供可持续的化学上循环解决方案.
科学领域:
- 材料科学 材料科学 材料科学
- 电化学 电化学 电化学
- 催化剂是一种催化剂.
背景情况:
- 电催化剂中的晶格氧气对C-H氧化至关重要,但由于不可移除的晶格位点,它与C-O-C键裂变作斗争.
- 在可持续化学中,高效地将木质素和塑料转化为有价值的化学物质仍然是一个重大挑战.
研究的目的:
- 开发一种可见光辅助的电化学方法,用于在现场配制可拆卸的晶格氧气位点.
- 为了创建一种氧化 (ESE-NiOOH) 电催化剂,能够裂解C-O-C键.
- 为了证明废弃物中的芳香醇和碳醇的高效转化为酸.
主要方法:
- 使用可见光辅助电化学来创建ESE-NiOOH,其可移动的晶格氧气站点.
- 现场表征被用来观察光诱导的晶格氧去除和再生.
- 理论计算确定了网状氧气促进的C-H键激活的机制.
主要成果:
- 在ESE-NiOOH催化剂证明高产量 (83-99%) 在转化芳香醇和碳酸到酸.
- 光照射对于去除晶格氧气和C-O-C键裂变至关重要,而再生则通过OH-补充发生.
- 一个"电化学漏斗"策略在升级混合芳香原料中实现了高达94%的产量.
结论:
- 格子氧位点的 in situ 移除再生是激活 C 键的可行策略.
- 这种方法可以选择性地将废弃的碳来源,如木质素和塑料转化为有价值的酸.
- 开发的方法为设计用于可持续化学转换的接口电催化剂开辟了新的途径.
相关概念视频
Thermal and Photochemical Electrocyclic Reactions: Overview
2.3K
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.
2.3K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.0K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
10.0K
Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
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
1.8K
Oxidative Cleavage of Alkenes: Ozonolysis
10.1K
In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
10.1K
Oxidation and Reduction of Organic Molecules
6.3K
Energy production within a cell involves many coordinated chemical pathways. Most of these pathways are combinations of oxidation and reduction reactions, which occur at the same time. An oxidation reaction strips an electron from an atom in a compound, and the addition of this electron to another compound is a reduction reaction. Because oxidation and reduction usually occur together, these pairs of reactions are called redox reactions.
The removal of an electron from a molecule, results in a...
The removal of an electron from a molecule, results in a...
6.3K
Oxidation-Reduction Reactions
64.5K
Oxidation–Reduction Reactions
64.5K


