NiOOHの活性部位を制御することによって,アディプ酸とサイクロヘキサノンの方向性電気合成
Yingshuai Jia1, Zheng Chen1, Boxu Gao1
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Fudan University, Shanghai 200433, P.R. China.
Journal of the American Chemical Society
|November 30, 2023
まとめ
現在,アディピック酸 (AA) とサイクロヘクサノン (CHN) の効率的な電気合成が可能である. 新しいニッケル酸化水素触媒は,サイクロヘクサノール脱水とCHN酸化により,これらの重要な化学物質の高収量を実現します.
科学分野:
- 電気化学
- 材料科学
- カタリシス
背景:
- ディカルボキシル酸 (例えばアディピック酸) とサイクルケトン (例えばサイクロヘクサノン) は,重要な産業化学物質である.
- 電気合成はそれらの生産のための有望な経路を提供するが,効率的な触媒とメカニズム的な理解は欠けている.
研究 の 目的:
- アディピック酸とサイクロヘクサノンの電気合成のための新しい触媒を開発する.
- これらの電気合成過程の背後にある反応機構を解明する.
主な方法:
- 自己溶解,インターフェース成長,電気化学的活性化を用いた単体msig/ea-NiOOH-Ni(OH) 2/NF触媒の製造.
- 相互接続されたNiOOHナノシートの立方体のようなアーキテクチャを含む触媒構造の特徴化.
- 触媒活動と反応経路を調査するための実験と理論の研究を組み合わせた.
主要な成果:
- サイクロヘクサノール (CHA) の脱水化により,サイクロヘクサノーン (CHN) の96. 5%の収量を達成した.
- CHN酸化によるアディピック酸 (AA) の93. 6%の収量を達成した.
- 酸素空位 (OV) のNi3+と過酸化物 (*OOH) が,CHA脱水とCHN酸化の両方を促進する鍵であることを実証した.
結論:
- 開発されたmsig/ea-NiOOH-Ni(OH) 2/NF触媒は,高純度化学物質の電気合成を効果的に促進する.
- 機理学的な洞察は,Ni3+と酸素の空白が触媒活動において果たす重要な役割を明らかにする.
- この研究は,重要な産業用化合物の標的型電気合成のための実行可能な戦略を提示しています.
さらに関連する動画
関連する概念動画
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.3K
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.
10.3K
Sharpless Epoxidation
4.0K
The conversion of allylic alcohols into epoxides using the chiral catalyst was discovered by K. Barry Sharpless and is known as Sharpless epoxidation. The use of a chiral catalyst enables the formation of one enantiomer of the product in excess. This chiral catalyst is mainly a chiral complex of titanium tetraisopropoxide and tartrate ester (specific stereoisomer). The stereoisomer used in the chiral catalyst dictates the formation of the enantiomer of the product. In other words, the use of...
4.0K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
5.9K
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.
5.9K
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
2.2K
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
2.2K
Preparation of Epoxides
7.8K
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of...
7.8K
Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control
2.6K
The addition of a hydrogen halide to 1,3-butadiene gives a mixture of 1,2- and 1,4-adducts. Since more substituted alkenes are more stable, the 1,4-adduct is expected to be the major product. However, the product distribution is strongly influenced by temperature; low temperature favors the 1,2-adduct, whereas the 1,4-adduct is predominant at high temperature.
2.6K


