Properties of metal–water interfaces studied from first principles

Schnur, Sebastian; Groß, Axel

doi:10.1088/1367-2630/11/12/125003

Cited by 323 publications

(396 citation statements)

References 77 publications

Supporting

Mentioning

352

Contrasting

Order By: Relevance

“…Exchange-correlation effects were incorporated within the generalized gradient approximation (GGA), using the exchangecorrelation functional by Perdew, Burke, and Ernzerhof (PBE) [40]. This functional consistently describes the properties of water at metal surfaces [41,42]. Geometry optimization studies were terminated when all forces on ions were less than 0.05 eV Å −1 .…”

Section: Methodsmentioning

confidence: 99%

Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

Eslamibidgoli

Eikerling

2016

Electrocatalysis

View full text Add to dashboard Cite

In this article, we propose a novel mechanism for the atomic-level processes that lead to oxide formation and eventually Pt dissolution at an oxidized Pt(111) surface. The mechanism involves a Pt extraction step followed by the substitution of chemisorbed oxygen to the subsurface. The energy diagrams of these processes have been generated using density functional theory and were analyzed to determine the critical coverages of chemisorbed oxygen for the Pt extraction and O ads substitution steps. The Pt extraction process depends on two essential conditions: (1) the local coordination of a Pt surface atom by three chemisorbed oxygen atoms at nearestneighboring fcc adsorption sites; (2) the interaction of the buckled Pt atom with surface water molecules. Results are discussed in terms of surface charging effects caused by oxygen coverage, surface strain effects, as well the contribution from electronic interaction effects. The utility of the proposed mechanism for the understanding of Pt stability at bimetallic surfaces will be demonstrated by evaluating the energy diagram of a Cu ML /Pt(111) near-surface alloy.

show abstract

Section: Methodsmentioning

confidence: 99%

Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

Eslamibidgoli

Eikerling

2016

Electrocatalysis

View full text Add to dashboard Cite

show abstract

“…Hydrogen bonds play a major role in surface termination orientation [66], solvent ordering [48,67] and work function [68] for solid-liquid interfaces. Therefore, it is important to get a better understanding of the impact of the hematite surface on the stability and orientation of the hydrogen bonds in water and at the surface.…”

Section: Hydrogen Bondsmentioning

confidence: 99%

Hematite(001)-liquid water interface from hybrid density functional-based molecular dynamics

Rudorff

Jakobsen

Rosso

et al. 2016

J. Phys.: Condens. Matter

View full text Add to dashboard Cite

The atom-scale characterisation of interfaces between transition metal oxides and liquid water is fundamental to our mechanistic understanding of diverse phenomena ranging from crystal growth to biogeochemical transformations to solar fuel production. Here we report on the results of large-scale hybrid density functional theory-based molecular dynamics simulations for the hematite(001)-liquid water interface. A specific focus is placed on understanding how different terminations of the same surface influence surface solvation. We find that the two dominant terminations for the hematite(001) surface exhibit strong differences both in terms of the active species formed on the surface and the strength of surface solvation. According to present simulations, we find that charged oxyanions (-O−) and doubly protonated oxygens (-OH) can be formed on the iron terminated layer via autoionization of neutral -OH groups. No such charged species are found for the oxygen terminated surface. In addition, the missing iron sublayer in the iron terminated surface strongly influences the solvation structure, which becomes less well ordered in the vicinity of the interface. These pronounced differences are likely to affect the reactivity of the two surface terminations, and in particular the energetics of excess charge carriers at the surface.

show abstract

“…49 Interestingly, the presence of hydroxyl groups (half-dissociated monolayer), such as those we find in tricalcium silicate, has been found to be more stable than a molecular monolayer in Ruthenium/water interfaces. 54 The icelike character of the tessellated water layer is quantified by examining the rotational and translational motion of the molecules. Rotations are characterized by the dipole moment reorientation dynamics.…”

Section: −2mentioning

confidence: 99%

Insight on Tricalcium Silicate Hydration and Dissolution Mechanism from Molecular Simulations

Manzano

Durgun

López‐Arbeloa

et al. 2015

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Hydration of mineral surfaces, a critical process for many technological applications, encompasses multiple coupled chemical reactions and topological changes, challenging both experimental characterization and computational modeling. In this work, we used reactive force field simulations to understand the surface properties, hydration, and dissolution of a model mineral, tricalcium silicate. We show that the computed static quantities, i.e., surface energies and water adsorption energies, do not provide useful insight into predict mineral hydration because they do not account for major structural changes at the interface when dynamic effects are included. Upon hydration, hydrogen atoms from dissociated water molecules penetrate into the crystal, forming a disordered calcium silicate hydrate layer that is similar for most of the surfaces despite wide-ranging static properties. Furthermore, the dynamic picture of hydration reveals the hidden role of surface topology, which can lead to unexpected water tessellation that stabilizes the surface against dissolution. KEYWORDS: dissolution, hydration, molecular dynamics, surface properties, water adsorption, calcium silicate ■ INTRODUCTIONThe hydration and dissolution of minerals is of crucial importance for a broad range of natural and synthetic phenomena: from the stability of minerals and rocks in watersheds and aquifers, 1 to hydrogen production and other heterogeneous catalytic reactions, 2,3 to the production, utilization, and ultimate degradation of building materials, 4 and to the durability of biomaterials, 5 to name only a few examples. The key properties at play during dissolution are controlled by interfacial reactions between water molecules and the solid surfaces, which can be probed experimentally via techniques such as AFM, vertical scanning interferometry (VSI), and the study of isotope exchange or solute fluxes to provide general information regarding the reaction rates or qualitative information about the formation of steps, pitches, and so on. 6 However, in many applications, much more control over the hydration and dissolution is desired, such as the ability to moderate the rate 7 or preferentially favor the dissolution of one crystal facet over other.8 To achieve such control, a deeper understanding of the molecular mechanisms governing hydration and dissolution is necessary.In this work, we use atomic-scale simulations to study the hydration of a calcium orthosilicate. We take a multistep approach, which is critical to piece together the relevant physical processes underlying hydration and dissolution. First, we analyze the surface energies and water molecule adsorption, extending beyond traditional approaches in order to obtain a more accurate picture of these properties. Next, we compare these surface properties with the results obtained from simulating a realistic hydration process over a period of 2 ns. We discuss the differences between the static and dynamic pictures and show that topological changes render the properties of the f...

show abstract

Properties of metal–water interfaces studied from first principles

Cited by 323 publications

References 77 publications

Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

Atomistic Mechanism of Pt Extraction at Oxidized Surfaces: Insights from DFT

Hematite(001)-liquid water interface from hybrid density functional-based molecular dynamics

Insight on Tricalcium Silicate Hydration and Dissolution Mechanism from Molecular Simulations

Contact Info

Product

Resources

About