铜复合体从空气中可逆取氧
Kurtis M Carsch1, Andrei Iliescu1, Ryan D McGillicuddy1
1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
Journal of the American Chemical Society
|October 21, 2021
概括
一种新型的铜复合物迅速从空气中吸收氧气,形成一个稳定的但可逆的铜-氧气附加物. 这一突破为开发新材料提供了洞察力.
科学领域:
- 协调化学
- 材料科学
- 无机化学
背景情况:
- 铜二氧化物复合物在生物系统和催化过程中至关重要.
- 开发稳定和可逆的二氧化铜添加剂仍然是一个重大挑战.
- 现有的分子二氧化铜复合体往往遭受不稳定和降解.
研究的目的:
- 合成和描述一种具有增强稳定性的新型二甲铜复合物.
- 研究二氧化碳与铜复合物的可逆结合.
- 探索铜二氧化物添加物的催化活性.
主要方法:
- 双皮林连接体及其铜复合体 (EMindL) Cu(N2) 的合成.
- 将复合物暴露在空气中以吸收溶液和固体中的氧气.
- 由此产生的二氧化铜添加物 (EMindL) Cu(O2) 的特性.
- 在各种条件下 (溶剂交换,热循环,氧化还原处理) 对二氧化物结合的可逆性进行研究.
- 对1,2-二化的催化氧化进行评估.
主要成果:
- 在暴露在空气中时,二氧化铜复合物 (EMindL) Cu(N2) 迅速且定量地形成稳定的铜-氧添加物 (EMindL) Cu(O2).
- (EMindL) Cu(O2) 添加物由于连接组而表现出无与伦比的空气和热稳定性.
- 二氧化结合在多个循环中是可逆的,证明了适应溶剂交换,热循环和氧化还原变化的能力.
- 该复合物催化了1,2-二基的氧化,通过可观测的 (EMindL) Cu ((H2O2) 中间体产生过氧化.
结论:
- 设计的二氧化连接剂使铜二氧化核心具有特殊的稳定性.
- 证明了可逆的二氧化结合和催化活性,突出显示了该复合物的潜力.
- 该研究提供了能够在环境条件下使用低坐标CuI吸收剂从空气中反向吸收氧气的新材料的设计原理.
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
相关概念视频
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
11.1K
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.
11.1K
02:04Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
6.3K
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
6.3K
01:20Radical Autoxidation
2.5K
The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
2.5K
01:17Oxidation of Phenols to Quinones
3.6K
In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
3.6K
02:21Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate
13.8K
Alkenes can be dihydroxylated using potassium permanganate. The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
13.8K
01:46Oxidative Cleavage of Alkenes: Ozonolysis
11.4K
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.
11.4K