A first-principles study of water adsorbed on flat and stepped silver surfaces

Lin, Xiaohang; Shao, Anchen; Hua, Minghao; Tian, Xuelei

doi:10.1039/d1cp04618g

Cited by 6 publications

(6 citation statements)

References 57 publications

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“…For simulations in the explicit solvation scheme, we have incorporated 12 explicit water molecules at the Pb(100) surface and 8 explicit water molecules at the Ag(100) surface, which are equivalent to the formation of one complete water layer at each surface, respectively. [42,50] In order to identify the transition states and activation barriers between reaction steps, we have utilized the climbing image nudged elastic band (CINEB) method. [51] Figure 3 illustrates HCOO* and COOH* reaction energy pathways at both Ag(100) and Pb(100) in vacuo.…”

Section: Dft Calculationsmentioning

confidence: 99%

Stay Hydrated! Impact of Solvation Phenomena on the CO₂ Reduction Reaction at Pb(100) and Ag(100) surfaces

et al. 2023

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This article presents a comprehensive computational study of the impact of solvation on the reduction reaction of CO2 to formic acid (HCOOH) and carbon monoxide (CO) at Pb(100) and Ag(100) surfaces. Results further the understanding of how solvation phenomena influence the adsorption energies of reaction intermediates. We applied an explicit solvation scheme harnessing a combined density functional theory (DFT)/microkinetic modeling approach for the CO2 reduction reaction. This approach reveals high selectivities for CO formation at Ag and HCOOH formation at Pb, successfully reconciling the disparity between ab initio calculations and experimental observations. Furthermore, the detailed analysis of adsorption energies of relevant reaction intermediates shows that the total number of hydrogen bonds formed by HCOO plays a primary role for the adsorption strength of intermediates and the electrocatalytic activity. Results emphasize the importance of explicit solvation for adsorption and electrochemical reaction phenomena on metal surfaces.

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Section: Dft Calculationsmentioning

confidence: 99%

Stay Hydrated! Impact of Solvation Phenomena on the CO₂ Reduction Reaction at Pb(100) and Ag(100) surfaces

et al. 2023

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“…However, the model does have limitations related to its significant simplification of the actual water structure near the solid/liquid interface. It has been reported, for example, that water overlayer configurations can have many structures other than the hexagonal lattice represented by the ice-like bilayer. ,,, Further, it is not obvious how to construct a static bilayer over complex surfaces with steps, kinks, and other defects. , In addition, the bilayer structure cannot adequately stabilize large adsorbates that cause significant distortion of the local water structure.…”

Section: Introductionmentioning

confidence: 99%

“…17,21,26,33 Further, it is not obvious how to construct a static bilayer over complex surfaces with steps, kinks, and other defects. 34,35 In addition, the bilayer structure cannot adequately stabilize large adsorbates that cause significant distortion of the local water structure. Statistical fluctuations in water configurations routinely occur in bulk liquids, and such variations propagate to the liquid−solid interface, as well.…”

Section: Introductionmentioning

confidence: 99%

Solvation Enthalpy Determination for Aqueous-Phase Reaction Adsorbates Using Ab Initio Molecular Dynamics-Based Structure Sampling

Chun,

Morankar,

Zeng

et al. 2024

J. Phys. Chem. C

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The interplay between covalent and noncovalent interactions at the solid−liquid interface strongly influences electrocatalytic reactions. Although methods to determine the former interactions have been rigorously developed, the latter are often described with static bilayer models or similarly approximate methods. In this study, we account for the disorder and dynamics at complex electrochemical interfaces by proposing a simple theory to estimate the enthalpy of solvation for adsorbed intermediates. In a strategy reminiscent of Born−Haber cycles, the enthalpy of solvation is expressed in terms of two subprocesses: vacancy creation by water reorganization and adsorbate interaction with solvent molecules. The magnitude of the solvation enthalpy is then determined as a mean valueof hydrated adsorbate-catalyst configurations obtained from simulated annealing with ab initio molecular dynamic (AIMD) simulations. This theory can be generalized for many combinations of surfaces and adsorbates. Its application improves treatment of energetics at electrified solid−liquid interfaces as well as corresponding structure−activity−stability predictions, as demonstrated for electrochemical oxygen reduction on Pt(111) and on Fe−N−C catalysts and for ethanol electrooxidation on Pt(111).

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“…We adopt a semiclassical model developed in refs − to treat the EDL within a grand canonical scheme. The corresponding atomistic EDL properties are sampled along AIMD trajectories calculated using a couple of explicit ions in thin water film on the metal electrode. ,− ,− ,− Both EDL models are about to be compared in terms of electrostatic potential, solvent orientation, and surface charging behaviors for the Pt(111)/water interface. We will identify the agreements and differences between the methods and connect the numerical results to experimentally accessible properties, e.g., surface charge, double-layer capacitance, and work function.…”

mentioning

confidence: 99%

Comparing Ab Initio Molecular Dynamics and a Semiclassical Grand Canonical Scheme for the Electric Double Layer of the Pt(111)/Water Interface

Huang

Zhang

et al. 2023

J. Phys. Chem. Lett.

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The theoretical modeling of metal/water interfaces centers on an appropriate configuration of the electric double layer (EDL) under grand canonical conditions. In principle, ab initio molecular dynamics (AIMD) simulations would be the appropriate choice for treating the competing water−water and water−metal interactions and explicitly considering the atomic and electronic degrees of freedom. However, this approach only allows simulations of relatively small canonical ensembles over a limited period (shorter than 100 ps). On the other hand, computationally efficient semiclassical approaches can treat the EDL model based on a grand canonical scheme by averaging the microscopic details. Thus, an improved description of the EDL can be obtained by combining AIMD simulations and semiclassical methods based on a grand canonical scheme. By taking the Pt(111)/water interface as an example, we compare these approaches in terms of the electric field, water configuration, and double-layer capacitance. Furthermore, we discuss how the combined merits of the approaches can contribute to advances in EDL theory.

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A first-principles study of water adsorbed on flat and stepped silver surfaces

Abstract: The structural, electronic and vibrational properties of a water layer on Ag(100) and Ag(511) have been studied by first principles calculations and ab initio molecular dynamics simulations. The most stable...

Cited by 6 publications

References 57 publications

Stay Hydrated! Impact of Solvation Phenomena on the CO₂ Reduction Reaction at Pb(100) and Ag(100) surfaces

Stay Hydrated! Impact of Solvation Phenomena on the CO₂ Reduction Reaction at Pb(100) and Ag(100) surfaces

Solvation Enthalpy Determination for Aqueous-Phase Reaction Adsorbates Using Ab Initio Molecular Dynamics-Based Structure Sampling

Comparing Ab Initio Molecular Dynamics and a Semiclassical Grand Canonical Scheme for the Electric Double Layer of the Pt(111)/Water Interface

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A first-principles study of water adsorbed on flat and stepped silver surfaces

Abstract: The structural, electronic and vibrational properties of a water layer on Ag(100) and Ag(511) have been studied by first principles calculations and ab initio molecular dynamics simulations. The most stable...

Cited by 6 publications

References 57 publications

Stay Hydrated! Impact of Solvation Phenomena on the CO2 Reduction Reaction at Pb(100) and Ag(100) surfaces

Stay Hydrated! Impact of Solvation Phenomena on the CO2 Reduction Reaction at Pb(100) and Ag(100) surfaces

Solvation Enthalpy Determination for Aqueous-Phase Reaction Adsorbates Using Ab Initio Molecular Dynamics-Based Structure Sampling

Comparing Ab Initio Molecular Dynamics and a Semiclassical Grand Canonical Scheme for the Electric Double Layer of the Pt(111)/Water Interface

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Stay Hydrated! Impact of Solvation Phenomena on the CO₂ Reduction Reaction at Pb(100) and Ag(100) surfaces

Stay Hydrated! Impact of Solvation Phenomena on the CO₂ Reduction Reaction at Pb(100) and Ag(100) surfaces