Grand-Canonical DFT Study of Hydrogen Peroxide Electro-Reduction: The Effect of Sn Alloying on Pt and Pd Activity
Abstract
The use of hydrogen peroxide in fuel cells is limited by the sluggish kinetics of its electroreduction using Pt or Pd as a cathode electrocatalyst. Sn is a possible candidate to activate those noble metals through surface alloying. To assess its effect on the hydrogen peroxide reduction reaction (HPRR) in acidic conditions, we studied the reaction mechanism of this reaction using the grand-canonical density functional theory (GC-DFT) approach, which explicitly accounts for the applied electrode potential. The reaction Gibbs free energy profiles were established as a function of the electrochemical potential on four surface models Pt(111), Pd(111), Pt ₂ Sn/Pt(111), and Pd₂Sn/Pd(111), considering two steps: (1) the dissociation of H₂O₂ into two OH intermediates, (2) OH hydrogenation. If considering only the thermodynamic overpotential, the best catalyst is PtSn with an overpotential of 0.58V. But this catalyst needs to overcome a barrier for the O-O scission that increases with the lowering of the potential finally reaching 0.33eV at 0V/SHE. Besides, the adsorption of H atom becomes favorable below 0.2V/SHE inducing a high barrier of 0.45eV for the OH hydrogenation through a hydrogen atom transfer mechanism. On the other hand, the Pd ₂ Sn(111)/Pd(111) surface alloys is the best candidate for the HPRR since the onset potential is around 0.98V/SHE and importantly the barrier for the O-O scission is below 0.25eV while the adsorption of H atom is disfavored by the presence of Sn which limits the poisoning of the surface in a wide range of potential.
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BibTeX
@article{gannouni2026grandcanonical,
title = {{Grand-Canonical DFT Study of Hydrogen Peroxide Electro-Reduction: The Effect of Sn Alloying on Pt and Pd Activity}},
author = {Anis Gannouni and Carine Michel},
journal = {Electrochimica Acta},
year = {2026},
month = oct,
doi = {10.1016/j.electacta.2026.149679},
url = {https://hal.science/hal-05781729v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Grand-Canonical DFT Study of Hydrogen Peroxide Electro-Reduction: The Effect of Sn Alloying on Pt and Pd Activity
AU - Anis Gannouni
AU - Carine Michel
PY - 2026
DA - 2026/10/06
JO - Electrochimica Acta
DO - 10.1016/j.electacta.2026.149679
UR - https://hal.science/hal-05781729v1
AB - The use of hydrogen peroxide in fuel cells is limited by the sluggish kinetics of its electroreduction using Pt or Pd as a cathode electrocatalyst. Sn is a possible candidate to activate those noble metals through surface alloying. To assess its effect on the hydrogen peroxide reduction reaction (HPRR) in acidic conditions, we studied the reaction mechanism of this reaction using the grand-canonical density functional theory (GC-DFT) approach, which explicitly accounts for the applied electrode potential. The reaction Gibbs free energy profiles were established as a function of the electrochemical potential on four surface models Pt(111), Pd(111), Pt ₂ Sn/Pt(111), and Pd₂Sn/Pd(111), considering two steps: (1) the dissociation of H₂O₂ into two OH intermediates, (2) OH hydrogenation. If considering only the thermodynamic overpotential, the best catalyst is PtSn with an overpotential of 0.58V. But this catalyst needs to overcome a barrier for the O-O scission that increases with the lowering of the potential finally reaching 0.33eV at 0V/SHE. Besides, the adsorption of H atom becomes favorable below 0.2V/SHE inducing a high barrier of 0.45eV for the OH hydrogenation through a hydrogen atom transfer mechanism. On the other hand, the Pd ₂ Sn(111)/Pd(111) surface alloys is the best candidate for the HPRR since the onset potential is around 0.98V/SHE and importantly the barrier for the O-O scission is below 0.25eV while the adsorption of H atom is disfavored by the presence of Sn which limits the poisoning of the surface in a wide range of potential.
SN - 0013-4686
ER -