从CO2促进选择性生成使用Mn(bpy) ((CO) 3Br作为电催化剂和三甲/异醇作为添加剂
Monica R Madsen1, Magnus H Rønne1, Marvin Heuschen1
1Carbon Dioxide Activation Center (CADIAC), Interdisciplinary Nanoscience Center, Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000 Aarhus C, Denmark.
Journal of the American Chemical Society
|November 23, 2021
概括
使用催化剂和三乙烯和异醇等添加剂有效地将二氧化碳 (CO2) 转化为酸 (HCOOH). 这种方法优化了有价值的化学产品的选择性和高效率.
科学领域:
- 电化学
- 催化剂
- 绿色化学
背景情况:
- 迫切需要将二氧化碳 (CO2) 转化为有价值的产品.
- 电催化减少二氧化碳提供了一个可持续的途径.
- 复合物可以作为减少二氧化碳的电催化剂.
研究的目的:
- 开发一种高效的电催化系统,将二氧化碳降解为酸 (HCOOH).
- 研究添加剂在控制产品选择性和反应途径方面的作用.
- 优化催化剂性能以获得高法拉达效率和低超电位.
主要方法:
- 使用催化剂,fac-Mn(bpy) ((CO) 3Br,电化学减少二氧化碳
- 系统地改变添加剂 (氨基和酒精) 以影响产品的选择性.
- 密度功能理论 (DFT) 计算以阐明反应机制.
主要成果:
- 通过使用三乙烯胺 (Et3N) 和异醇 (iPrOH) 作为添加剂选择性生产HCOOH而不是CO.
- 在260mV的超电位下,HCOOH的法拉达效率达到了59 ± 1%.
- 在2M Et3N和iPrOH的560 mV超电位下最大化法拉达效率为71 ± 3%.
- 证明了氨基结构在确定HCOOH选择性的关键作用.
结论:
- 介绍了一种简单的二氧化碳转化为HCOOH的电化学方法.
- 催化剂与特定添加剂的组合使其具有很高的选择性和效率.
- 了解添加效应是设计用于二氧化碳利用的先进电催化系统的关键.
相关概念视频
01:15α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
3.2K
The method to achieve α-brominated carboxylic acids using a mixture of phosphorus tribromide and bromine is known as the Hell–Volhard–Zelinski reaction. The reaction is catalyzed by phosphorus tribromide, which can be used directly or produced in situ from red phosphorus and bromine. The mechanism comprises PBr3 catalyzed conversion of acid to acid bromide and hydrogen bromide. The acid bromide enolizes to its enol form in the presence of HBr. The nucleophilic enol attacks the...
3.2K
01:20Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview
18.7K
The Fischer esterification reaction was developed by the German chemist Emil Fischer in 1895. It is a condensation reaction between carboxylic acids and alcohols in an acidic medium to give esters and water.
18.7K
01:13Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism
8.3K
Carboxylic acids react with alcohols to yield esters via an acid-catalyzed condensation reaction called Fischer esterification. This is a nucleophilic acyl substitution reaction that proceeds via a tetrahedral intermediate, where a water molecule is eliminated as the leaving group.
8.3K
01:07Preparation of Acid Anhydrides
3.4K
One of the methods for preparing symmetrical or unsymmetrical acid anhydrides involves the treatment of acid chlorides with the sodium salt of carboxylic acids. The reaction proceeds via a nucleophilic acyl substitution.
The carboxylate ion acts as a nucleophile that attacks the carbonyl carbon of the acid chloride to form a tetrahedral intermediate. Subsequently, the re-formation of the carbonyl group with the loss of the chloride ion as a leaving group leads to the formation of an acid...
The carboxylate ion acts as a nucleophile that attacks the carbonyl carbon of the acid chloride to form a tetrahedral intermediate. Subsequently, the re-formation of the carbonyl group with the loss of the chloride ion as a leaving group leads to the formation of an acid...
3.4K
01:13Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
3.2K
Hydrolysis of esters under acidic conditions proceeds through a nucleophilic acyl substitution. In the presence of excess water, the reaction proceeds in a reversible manner, forming carboxylic acids and alcohols.
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
3.2K
01:31Preparation of Carboxylic Acids: Overview
2.8K
There are various methods for the preparation of carboxylic acids. For example, oxidation of primary alcohols or aldehydes using strong oxidizing agents results in a carboxylic acid. Aldehydes can also be oxidized in the presence of mild oxidizing agents.
2.8K