Water adsorption on metal surfaces: an electrochemical viewpoint

Sass, JK; Kretzschmar, K.; Holloway, S.

doi:10.1016/0042-207x(81)90043-9

Cited by 32 publications

(6 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Here, an important step forward was achieved by W. N. Hansen, when he showed that electrodes could be emersed with their electric double layer intact (see Section 3) 53. The studies of emersed electrodes that followed and, to a lesser extent, the double‐layer simulation studies (an attempt to compose the electric double layer under UHV conditions by adsorbing, for example, water and metal ions54) yielded a wealth of information about bare and adsorbate‐covered electrodes. Examples are the study of surface reconstruction55 or ordered adsorption occurring during metal‐monolayer formation 37, 56…”

Section: The Experimental Basis Of An Electrochemical Surface Sciencementioning

confidence: 99%

Electrochemical Surface Science

Kolb

2001

Angew. Chem. Int. Ed.

281

111

View full text Add to dashboard Cite

The last 30 years have seen remarkable changes in interfacial electrochemistry, particularly in the kind of questions that were addressed in electrochemical studies. Ever since classical surface science, traditionally performed under ultrahigh vacuum conditions, has succeeded in describing surfaces and surface reactions on a molecular level, electrochemists longed for a microscopic understanding of the solid/electrolyte interface and, at the same time, searched widely for new experimental ways to reach that goal. Herein, studies are described concerning the structure and the dynamics of bare and adsorbate‐covered electrode surfaces and of metal deposition as a simple, yet important, electrochemical process. In all these cases, the scanning tunneling microscope plays a pivotal role emphasizing the surface‐science approach to the problems.

show abstract

Section: The Experimental Basis Of An Electrochemical Surface Sciencementioning

confidence: 99%

Electrochemical Surface Science

Kolb

2001

Angew. Chem. Int. Ed.

281

111

View full text Add to dashboard Cite

show abstract

“…Elucidating the binding and assembly of these molecules at surfaces has relevance to a number of fields, such as electrochemistry, environmental chemistry, fluid transport, and heterogeneous catalysis. [1][2][3][4] It is also a source of general insight into molecular self-assembly at interfaces and the fundamental nature of interfacial hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

Murphy

Carrasco

Lawton

et al. 2014

The Journal of Chemical Physics

View full text Add to dashboard Cite

Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

show abstract

“…12,13,28,34 -42 No experimental evidence for dissociation of water on the clean metal surfaces has been found. 40 Based on experimental results a simple model for the water adlayer on a metal surface was proposed by Sass et al 43 and Doering and Madey 44 already in the beginning of the 1980s ͓Figs. 1͑a͒ and 1͑b͔͒.…”

Section: Introductionmentioning

confidence: 99%

Ab initio studies of a water layer at transition metal surfaces

Vassilev

Santen

Koper

2005

The Journal of Chemical Physics

View full text Add to dashboard Cite

This paper presents a detailed study of a water adlayer adsorbed on Pt(111) and Rh(111) surfaces using periodic density functional theory methods. The interaction between the metal surface and the water molecules is assessed from molecular dynamics simulation data and single point electronic structure calculations of selected configurations. It is argued that the electron bands around the Fermi level of the metal substrate extend over the water adlayer. As a consequence in the presence of the water layer the surface as a whole still maintains its metallic conductivity—a result of a crucial importance for understanding the process of electron transfer through the water/metal interface and electrochemical reactions in particular. Our results also indicate that there exists a weak bond between the hydrogen of the water and the Rh metal atoms as opposed to the widespread (classical) models based on purely repulsive interaction. This suggests that the commonly used classical interactions potentials adopted for large scale molecular dynamics simulations of water/metal interfaces may need revision. Two adsorption models of water on transition metals with the OH bonds pointing towards or away of the surface are also examined. It is shown that due to the very close values of their adsorption energies one should consider the real structure of water on the surface as a mixture of these simple “up” and “down” models. A model for the structure of the adsorbed water layer on Rh(111) is proposed in terms of statistical averages from molecular dynamics simulations.

show abstract

Water adsorption on metal surfaces: an electrochemical viewpoint

Cited by 32 publications

References 13 publications

Electrochemical Surface Science

Electrochemical Surface Science

Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

Ab initio studies of a water layer at transition metal surfaces

Contact Info

Product

Resources

About