Energy–entropy competition in cation–hydroxyl interactions at the liquid water–Pt(111) interface

Kristoffersen, Henrik H.; Chan, Karen; Vegge, Tejs; Hansen, Heine Anton

doi:10.1039/c9cc07769c

Cited by 31 publications

(29 citation statements)

References 29 publications

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“…However, there are still questions that remain to be addressed. In particular, accurately modelling the dynamic nature of the water layer at ambient conditions presents a major obstacle due to the high computational cost of ab initio based methods 16,17 . To circumvent this problem, the majority of such studies do not include the liquid water layer explicitly.…”

Section: Introductionmentioning

confidence: 99%

Is the water/Pt(111) interface ordered at room temperature?

Mikkelsen

Schiøtz

Vegge

et al. 2021

The Journal of Chemical Physics

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The structure of the water/Pt(111) interface has been a subject of debate over the past decades. Here, we report the results of a room temperature molecular dynamics study based on neural network potentials, which allow us to access long time scale simulations while retaining ab initio accuracy. We find that the water/Pt(111) interface is characterized by a double layer composed of a primary, strongly bound adsorption layer with a coverage of ∼ 0.15ML, which is coupled to a secondary, weakly bound adsorption layer with a coverage of ∼ 0.58ML. By studying the order of the primary adsorption layer we find that there is an effective repulsion between the adsorbed water molecules, which gives rise to a dynamically-changing, semi-ordered interfacial structure, where the water molecules in the primary adsorption layer are distributed homogeneously across the interface forming frequent hydrogen bonds to water molecules in the secondary adsorption layer. We furthermore show that these conclusions are beyond the time scales accessible to ab initio molecular dynamics.

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Section: Introductionmentioning

confidence: 99%

Is the water/Pt(111) interface ordered at room temperature?

Mikkelsen

Schiøtz

Vegge

et al. 2021

The Journal of Chemical Physics

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“…For the well solvated cases of A1 and A2 and their variations, the dissociation barrier averages around 0.2 eV and the fluctuation is within 0.1 eV which is comparable with the error reported in a recent AIMD study on the interaction energy between cation and OH* on Pt(111) in the presence of H2O molecules. 1 The dissociation of O2* on Pt(111) is facile in alkaline media, which is similar to the O2* dissociation in the acidic media. 2 By adding charges to the slab, we further explore the variation in the O2* dissociation barrier as the electrode potential is changed.…”

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confidence: 79%

Cross Sphere Electrode Reaction: the Case of Hydroxyl Desorption during the Oxygen Reduction Reaction on Pt(111) in Alkaline Media

Liu²

2021

Preprint

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Hydroxide ion is a common electrolyte when electrode reactions take place in alkaline media. In the case of oxygen reduction reaction on Pt(111), we demonstrate by ab initio molecular dynamics calculations, that the desorption of hydroxyl (OH*) from the electrode surface to form a solvated OH− is a cross sphere process, with the reactant OH* in the inner sphere and the product OH− directly generated in the aqueous outer sphere. Such a mechanism is distinct from the typical inner sphere and outer sphere reactions. It is dictated by the strong hydrogen bonding interactions between a hydroxide ion and water molecules and facilitated by proton transfer through solvation layers. It should play a significant role whenever OH* desorption, or its reverse, OH− adsorption, is involved in an electrochemical reaction

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“…372 We point out that simple solvation models are preferred even today, [373][374][375] while there is increasing number of researches that adopt the conventional periodicinterface-model where the associated boundary problem is reduced by incorporating more water molecules and solvated ions into the computational cell. 64,[376][377][378]…”

Section: Summary and Remarks For This Sectionmentioning

confidence: 99%

Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid–liquid interfaces

Sakaushi

Kumeda

Hammes‐Schiffer

et al. 2020

Phys. Chem. Chem. Phys.

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Energy–entropy competition in cation–hydroxyl interactions at the liquid water–Pt(111) interface

Abstract: At water–Pt(111) interfaces, cation–*OH interactions are found to consist of both internal energy stabilizations and entropy costs emphasizing the complexity of such systems.

Cited by 31 publications

References 29 publications

Is the water/Pt(111) interface ordered at room temperature?

Is the water/Pt(111) interface ordered at room temperature?

Cross Sphere Electrode Reaction: the Case of Hydroxyl Desorption during the Oxygen Reduction Reaction on Pt(111) in Alkaline Media

Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid–liquid interfaces

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