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Synergistic cation-facet effects boost alkaline hydrogen evolution kinetics on stepped Pt surfaces.
Qingqing Zhang1, Pengfei Sun2, Haobo Li3
1State Key Laboratory of Solidification Processing, School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an, Shaanxi, PR China.
Communications Chemistry
|February 2, 2026
Summary
Alkali cations accelerate hydrogen evolution reaction (HER) on platinum. Stepped surfaces stabilize cations, enhancing water dissociation and reaction rates compared to flat surfaces.
Area of Science:
- Electrochemistry
- Materials Science
- Computational Chemistry
Background:
- Electrocatalytic hydrogen production is key for clean energy.
- Understanding electrolyte-catalyst interactions is vital for improving reaction kinetics.
Purpose of the Study:
- To investigate the atomic-scale synergy between alkali cations and platinum surface structure.
- To elucidate how these interactions accelerate the alkaline hydrogen evolution reaction (HER).
Main Methods:
- Combined constant-potential density functional theory (DFT) simulations.
- Ab initio molecular dynamics (AIMD) simulations.
Main Results:
- Stepped Pt(311) surfaces stabilize Na+ cations at step edges, forming a Pt-H2O-Na+(H2O)x adduct.
- Cation proximity on Pt(311) enhances the interfacial electric field, lowering the Volmer step activation energy by 0.14 eV.
- Pt(111) terraces show distant cation solvation, minimally impacting HER kinetics.
Conclusions:
- Cation-facet cooperativity is a critical design principle for HER catalysis.
- Atomic-scale control of surface geometry and the electrochemical double layer can overcome kinetic limitations.
- This study provides insights into optimizing electrocatalysts for hydrogen production.
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