Double-Stranded Water on Stepped Platinum Surfaces

Kolb, Manuel J.; Farber, Rachael G.; Derouin, Jonathan; Badan, Cansin; Calle‐Vallejo, Federico; Juurlink, Ludo B. F.; Killelea, Daniel R.; Koper, Marc T. M.

doi:10.1103/physrevlett.116.136101

Cited by 46 publications

(67 citation statements)

References 36 publications

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“… 13 To examine the effects of solvation near the electrode surface, we examined hydrogen adsorption in the presence of water molecules adsorbed next to the step edge, hydrogen bonded in the single-stranded water structure, and hydroxide adsorption with coadsorbed water molecules in the double-stranded water structure. 29 These structures were identified previously to give adsorption potentials that compare well with experiment for adsorption on the Pt(553) surface. 13 This work goes beyond our prior examination with DFT of adsorption on the Pt(533) surface, 10 and we now more fully solvate the step edge and examine lower coverages of adsorbed hydroxyl and adsorbed cation, such that we can examine cation coverages present at intermediate pH.…”

Section: Resultsmentioning

confidence: 55%

Effect of Step Density and Orientation on the Apparent pH Dependence of Hydrogen and Hydroxide Adsorption on Stepped Platinum Surfaces

et al. 2018

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The effect of the alkali-metal cation (Li+, Na+, K+, and Cs+) on the non-Nernstian pH shift of the Pt(554) and Pt(533) step-associated voltammetric peak is elucidated over a wide pH window (1–13), through computation and experiment. In conjunction with our previously reported study on Pt(553), the non-Nernstian pH shift of the step-induced peak is found to be independent of the step density and the step orientation. In our prior work, we explained the sharp peak as due to the exchange between adsorbed hydrogen and hydroxyl along the step and the non-Nernstian shift as a result of the adsorption of an alkali-metal cation and its subsequent weakening of hydroxyl adsorption. Our density functional theory results support this same mechanism on Pt(533) and capture the effect of alkali-metal cation identity and alkali cation coverage well, where increasing electrolyte pH and cation concentration leads to increased cation coverage and a greater weakening effect on hydroxide adsorption. This work paints a consistent picture for the mechanism of these effects, expanding our fundamental understanding of the electrode/electrolyte interface and practical ability to control hydrogen and hydroxyl adsorption thermodynamics via the electrolyte composition, important for improving fuel cell and electrolyzer performance.

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Section: Resultsmentioning

confidence: 55%

Effect of Step Density and Orientation on the Apparent pH Dependence of Hydrogen and Hydroxide Adsorption on Stepped Platinum Surfaces

et al. 2018

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“…27 The many experimental observations have prompted theoretical investigations on water structure on elemental metals, 17,18,[28][29][30][31][32][33][34][35] oxides, 25,[36][37][38][39][40] bimetallic alloys, 26,41 and stepped transition metal facets. 32,[42][43][44] Recent theoretical work has provided a systematic understanding of of how various surface properties affect surface binding of water. 45 Several studies have also investigated the effects of explicitly including pH.…”

Section: Introductionmentioning

confidence: 99%

Solvent–Adsorbate Interactions and Adsorbate-Specific Solvent Structure in Carbon Dioxide Reduction on a Stepped Cu Surface

et al. 2019

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“…12,[15][16][17] For water, the most common solvent, different adsorbed frameworks depending on the surface morphology are observed. [18][19][20][21][22] Such "water bilayers" modify ADS G Δ of reaction intermediates: several studies have shown the importance of *OH and *OOH solvation by water for computational models of the oxygen reduction reaction (ORR) to be quantitatively comparable to experiments. 14,19,[23][24][25][26] Explicit ice-like hexagonal water layers over pristine close-packed surfaces of transition metals are typically used (Figure 1b).…”

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confidence: 99%

Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles

et al. 2019

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Electrocatalysts are mainly characterized by their intrinsic adsorption properties. However, the observed electrocatalytic activity ultimately results from the interplay between such properties and various additional interactions within the electrified solid-liquid interface. One of such phenomena is solvation, which can substantially affect the stability of adsorbates. The incorporation of solvation in computational electrocatalysis models can be fully implicit (inaccurate for H-bonded adsorbates), fully explicit (challenging computation of free energies), or embedded. Here we show that without any need for explicit or implicit media, a micro-solvation approach with just 3 water molecules captures the contribution of coadsorbed water to the adsorption energies of *OH and *OOH (two important adsorbates for oxygen reduction) on platinum nanoparticles of various sizes. The approach enables an accurate yet inexpensive explicit modeling of solvent-adsorbate interactions in nanoparticles, and the calculation of solvation corrections, estimated as 0.59 0.14 eV − ± and 0.47 0.13 eV − ± for *OH and *OOH adsorption on Pt.

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Double-Stranded Water on Stepped Platinum Surfaces

Cited by 46 publications

References 36 publications

Effect of Step Density and Orientation on the Apparent pH Dependence of Hydrogen and Hydroxide Adsorption on Stepped Platinum Surfaces

Effect of Step Density and Orientation on the Apparent pH Dependence of Hydrogen and Hydroxide Adsorption on Stepped Platinum Surfaces

Solvent–Adsorbate Interactions and Adsorbate-Specific Solvent Structure in Carbon Dioxide Reduction on a Stepped Cu Surface

Affordable Estimation of Solvation Contributions to the Adsorption Energies of Oxygenates on Metal Nanoparticles

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