Mechanistic Insights into the Unique Role of Copper in CO₂ Electroreduction Reactions

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• 作者：Dr. Shan Ping Liu ; Prof. Dr. Ming Zhao ; Prof. Dr. Wang Gao and Prof. Dr. Qing Jiang
• 刊名：ChemSusChem
• 出版年：2017
• 出版时间：January 20, 2017
• 年：2017
• 卷：10
• 期：2
• 页码：387-393
• 全文大小：972K
• ISSN：1864-564X

文摘

Cu demonstrates a unique capability towards CO₂ electroreduction that can close the anthropogenic carbon cycle; however, its reaction mechanism remains elusive, owing to the obscurity of the solid–liquid interface on Cu surfaces where electrochemical reactions occur. Using a genetic algorithm method in addition to density functional theory, we explicitly identify the configuration of a water bilayer on Cu(2 1 1) and build electrochemical models. These enable us to reveal a mechanistic picture for CO₂ electroreduction, finding the key intermediates CCO* for the C₂H₄ pathway and CH* for the CH₄ pathway, which rationalize a series of experimental observations. Furthermore, we find that the interplay between the Cu surfaces, carbon monomers, and water network (but not the binding of CO*) essentially determine the unique capability of Cu towards CO₂ electroreduction, proposing a new and effective descriptor for exploiting optimal catalysts.