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Subsurface hydrogen as a hidden driver of copper surface reconstruction in CO2 electroreduction
Siwang Zhang1, Hang-Biao Lv1, Zhong-Zhang Shi1
1College of Energy, State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, College of Materials, Institute of Artificial Intelligence, School of Life Sciences, Xiamen University, Xiamen 361000, China.
Surface roughening in copper electrocatalysis is driven by hydrogen intermediates, particularly on (100) facets. This study reveals a new mechanism for copper catalyst instability and proposes alloying strategies for enhanced durability.
Area of Science:
- Surface science
- Computational chemistry
- Electrocatalysis
Background:
- Copper (Cu) catalysts are crucial for CO2 electroreduction, but their surface reconstruction under reaction conditions is not fully understood.
- Reaction intermediates like adsorbed hydrogen (*H) and carbon monoxide (*CO) significantly influence Cu surface dynamics.
Purpose of the Study:
- To investigate the atomic-scale mechanisms of *CO- and *H-induced surface roughening on different Cu facets.
- To elucidate the role of surface hydrogen (*Hsur) and subsurface hydrogen (*Hsub) in Cu surface reconstruction.
Main Methods:
- Integration of machine-learning interatomic potentials with large-scale grand canonical Monte Carlo simulations.
- Systematic investigation of surface roughening across various Cu facets, including (100) and (111)-like surfaces.
Main Results:
- High *Hsur coverage promotes *Hsub incorporation on (100)-dominated Cu facets, leading to surface roughening.
- *H-induced hexagonal surface reconstruction on (100) facets facilitates *Hsub migration due to geometric effects.
- *Hsub alone can induce Cu adatom formation, revising the understanding of Cu surface evolution.
Conclusions:
- Facet-dependent surface reconstruction is a key factor in Cu catalyst stability during CO2 electroreduction.
- Alloying Cu with low hydrogen affinity metals (Zn, Al, Ga) can suppress *Hsur incorporation and improve catalyst durability.
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