高温高圧下での銅触媒CO₂電気還元におけるC-C結合生成のための代替連鎖成長機構
Rafaël E Vos1, Pengfei Sun1,2, Daniel Schauermann1
1Leiden Institute of Chemistry, Leiden University, Leiden, Netherlands.
Abstract:
Future practical applications of the electrochemical CO2 reduction reaction will probably involve the use of higher pressures and temperatures. However, most research on the copper-catalysed electrochemical CO2 reduction reaction-the most widely studied system due to its C-C coupling ability-is typically performed under ambient conditions, and hence the mechanistic conclusions drawn also pertain to those conditions. Using a custom high-pressure, high-temperature electrochemical cell, we show here that on copper electrodes, the C-C coupling mechanism changes from the typical CO dimerization mechanism at low temperatures to a Fischer-Tropsch-like chain growth mechanism at temperatures above 125 °C (also requiring higher pressure). These results show that temperature and pressure are crucial parameters to consider in applied and mechanistic studies of the electrochemical reduction of CO2 because they can open up alternative reaction pathways and alter known mechanisms.
関連する概念動画
Thermal and Photochemical Electrocyclic Reactions: Overview
Thermal Electrocyclic Reactions: Stereochemistry
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.
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Carbon-dioxide Fixation
The Calvin Benson Cycle
Electron Transport Chain: Complex III and IV


