H-Induced Restructuring on Cu(111) Triggers CO Electroreduction in an Acidic Electrolyte
Dongfang Cheng1, Anastassia N Alexandrova2,3,4, Philippe Sautet1,2,4
1Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, California 90095, United States.
The Journal of Physical Chemistry Letters
|January 23, 2024
Summary
Hydrogen adatoms on copper surfaces initiate CO2 reduction (CO2RR) in acidic media, overcoming hydrogen evolution competition. This discovery reveals new active sites and reaction pathways for CO2RR.
Area of Science:
- Electrochemistry
- Surface Science
- Computational Chemistry
Background:
- The electroreduction of carbon dioxide (CO2RR) is challenging in acidic media due to competing hydrogen evolution reactions (HER).
- Understanding the fundamental mechanisms of CO2RR on metal surfaces is crucial for developing efficient catalysts.
Purpose of the Study:
- To investigate a novel mechanism for CO2RR in acidic environments facilitated by H-induced adatoms on Cu(111).
- To elucidate the role of these adatoms in creating active sites for CO adsorption and reduction.
Main Methods:
- First-principles calculations.
- Grand canonical surface state population analysis.
- Ensemble-based kinetic modeling.
Main Results:
- H-induced Cu adatoms on Cu(111) act as key sites for initiating CO2RR in acidic conditions.
- These adatoms enhance both HER and CO2RR, with their contributions varying with electrode potential and pH.
- Surface state dynamics and electrochemical activity are intricately linked, influencing active site formation and reaction kinetics.
Conclusions:
- The formation of H-induced adatoms provides a new pathway for CO2RR on Cu(111) in acidic media.
- This mechanism highlights the potential-dependent nature of active sites and reaction kinetics.
- The findings offer insights into optimizing catalysts for efficient CO2 conversion.
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