Restructuring and Activation of Cu(111) under Electrocatalytic Reduction Conditions

Autor: Dongfang Cheng, Ziyang Wei, Zisheng Zhang, Peter Broekmann, Anastassia N. Alexandrova, Philippe Sautet
Rok vydání: 2023
Předmět:
Zdroj: Angewandte Chemie International Edition. 62
ISSN: 1521-3773
1433-7851
DOI: 10.1002/anie.202218575
Popis: The dynamic restructuring of Cu surfaces in electroreduction conditions is of fundamental interest in electrocatalysis. We decode the structural dynamics of a Cu(111) electrode under reduction conditions by joint first-principles calculations and operando electrochemical scanning tunneling microscopy (ECSTM) experiments. Combining global optimization and grand canonical density functional theory, we unravel the potential- and pH-dependent restructuring of Cu(111) in acidic electrolyte. At reductive potential, Cu(111) is covered by a high density of H atoms and, below a threshold potential, Cu adatoms are formed on the surface in a (4×4) superstructure, a restructuring unfavorable in vacuum. The strong H adsorption is the driving force for the restructuring, itself induced by electrode potential. On the restructured surface, barriers for hydrogen evolution reaction steps are low. Restructuring in electroreduction conditions creates highly active Cu adatom sites not present on Cu(111).
Databáze: OpenAIRE
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