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O2 Reduction Stimulates Adatom Generation on Cu(111) Catalyzing Hydrogen Evolution
David Raciti1, Zisheng Zhang2,3, Ally Guo1
1Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States.
Journal of the American Chemical Society
|February 11, 2026
Summary
Surface hydride formation on Cu(111) is altered by oxygen, impacting oxygen reduction and hydrogen evolution reactions. Coupled adsorbates dynamically restructure the copper surface, creating new active sites and affecting catalyst stability.
Area of Science:
- Surface electrochemistry
- Electrocatalysis
- Materials science
Background:
- Copper (Cu) is a key electrocatalyst for various reactions.
- Understanding surface dynamics is crucial for catalyst design.
- Electrochemical mass spectrometry (EC-MS) offers in-situ insights.
Purpose of the Study:
- Investigate coupled surface hydride formation, oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER) on Cu(111).
- Elucidate the role of oxygen in restructuring Cu(111) surfaces.
- Determine the impact of surface restructuring on catalytic activity and stability.
Main Methods:
- Electrochemical mass spectrometry (EC-MS) for in-situ analysis.
- Density functional theory (DFT) and molecular dynamics (MD) simulations.
- Grand canonical free-energy calculations.
Main Results:
- Surface hydride formation on Cu(111) is influenced by electrode cycling and residual oxides.
- Oxygen introduction perturbs hydride formation and accelerates HER kinetics.
- Coadsorption of H and ORR intermediates drives Cu(111) restructuring, forming new active sites.
Conclusions:
- Coupled adsorbates dynamically restructure Cu(111) under electrochemical bias.
- Surface restructuring generates novel active sites, modulating ORR and HER kinetics.
- Findings have direct implications for Cu electrocatalyst performance and stability.
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