Halide adsorption on close-packed metal electrodes

Roman, Tanglaw; Gossenberger, Florian; Forster-Tonigold, Katrin; Groß, Axel

doi:10.1039/c4cp00237g

Cited by 66 publications

(79 citation statements)

References 31 publications

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“…1(c)-1(g), energetically favorable con gurations of Cl atoms on the surface for each coverage Θ are depicted. The Cl atoms prefer to adsorb at the atop sites at lower coverage, which is consistent with the results obtained by Zhu and Wang 22) and Liu et al 28) The atop-site adsorption is an unusual preference because halogens are known to preferentially adsorb at hollow sites on the metal surface with a few exceptions such as uorine adsorption onto Pt(111) 16,37) . At higher coverage, the Cl atoms were stably adsorbed at a combination of atop and fcc sites for 1/2 ML and at a combination of atop, fcc, and hcp sites for 3/4 ML.…”

Section: Energetic Properties: Adsorption Onto Al(111)supporting

confidence: 88%

“…Density functional theory (DFT) 10) is a powerful theoretical tool for elucidating the chemical nature of materials on the atomic scale. Many DFT investigations have been published on the surface structure of halogen adsorption onto a metal surface, especially for noble metals [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] . Optimization of the adsorption structures of Cl − , Br − , and I − as well as their harmonic vibration frequencies on the (100) surface of Cu, Ag, and Au have been studied by Ignaczak and Gomes 17) .…”

Section: −mentioning

confidence: 99%

“…E chem de ned in eq. 3as a function of coverage is shown 48) , 4.051 16) 4.02 49) B 0 (GPa) 79.2 70.5 48) 81.3 49) Al(111) 48) , 4.07 22) , 4.04 16) 4.26 22) , 4.48 50) , 4.24 51) σ (J/m 2 ) 0.86 0.90 0.88 0.75 50) 1.16 51) , 1.14 52) ∆d 12 (%) +1.06 +1.59 +1.21 +1.06 48) +1.7 ± 0.3 53) ∆d 23 (%) −0.22 −0.37 −0.26 −1.53 48) +0.5 ± 0.7 53) Fig. 1 (a) Initial slab model in which Cl atom is placed 3 Å above the Al(111) surface.…”

Section: Energetic Properties: Adsorption Onto Al(111)unclassified

“…The adsorption of electronegative adsorbates, such as halogens, onto metal surfaces has been observed to change in the work function 20,22,[42][43][44][45][46] . Roman et al proposed a mechanism that can explain the change in the work function and the formation of an electrostatic dipole moment when a halogen is adsorbed on a metal substrate 16) . They considered the adsorption of F, Cl, Br, and I into various metal surfaces.…”

Section: Electronic Properties: Adsorption Onto Al(111) Surfacementioning

confidence: 99%

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First-Principles Study of Chlorine Adsorption on Clean Al(111)

Yamashita

Nunomura

2017

Mater. Trans.

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A density functional theory model is used to investigate the structural, thermodynamic, and electronic properties of chlorine atoms adsorbed on the Al(111) surface within a supercell approach for chlorine coverages of 1/4, 1/3, 1/2, 3/4, and 1 ML. The largest bond length is observed for an atop, hcp, and fcc mixed structure at 3/4 ML coverage. Analysis of the adsorption free energy reveals that the chlorine coverage of 3/4 ML is the most thermodynamically stable over the widest range of chlorine chemical potential and that the coverage of 1 ML is thermodynamically unstable. The electronic charge density distributions, the change in the work function induced by adsorption, and the corresponding electrostatic dipole moment are also calculated. Atop-site adsorption is shown to induce charge transfer and the formation of a dipole structure for low coverage, and the charge transfer decreases with increasing coverage. Surface bonding is investigated using the projected density of states, and aluminum and chlorine 3p-orbitals are shown to be important in Al-Cl bond formation.

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Section: Energetic Properties: Adsorption Onto Al(111)supporting

confidence: 88%

Section: −mentioning

confidence: 99%

Section: Energetic Properties: Adsorption Onto Al(111)unclassified

Section: Electronic Properties: Adsorption Onto Al(111) Surfacementioning

confidence: 99%

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First-Principles Study of Chlorine Adsorption on Clean Al(111)

Yamashita

Nunomura

2017

Mater. Trans.

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“…7,10,25,43 The sequence of specific adsorbability of halides at many metals, including Hg, Bi, Sb, Cd, Zn, Au, Ag, from aqueous solutions is: Cl − < Br − < I − . 7,25,[42][43][44][45][46][47][48] In order to elucidate the nature of electrode-ion bonding we conducted DFT calculations. The changes in the work function values due to the adsorption of halides (F, Cl, Br, I) on Au(111) and Bi(111) surfaces are shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Investigation of 1-Ethyl-3-methylimidazolium Bromide and Tetrafluoroborate Mixture at Bi(111) Electrode Interface

Siimenson

Lembinen

Oll

et al. 2016

J. Electrochem. Soc.

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Electrochemical characterization of the interface between Bi(111) surface and ionic liquid mixtures of 1-ethyl-3-methylimidazolium tetrafluoroborate with 1-ethyl-3-methylimidazolium bromide (EMImBF 4 + x% EMImBr) has been evaluated by using the electrochemical impedance spectroscopy, cyclic voltammetry methods and density functional theory calculations. Dependence of the experimental data on the bromide concentration and on the electrode potential has been analyzed. Comparison of adsorption data with Bi(111) | EMImBF 4 + x% EMImI interface shows that adsorption activity of halide ions from EMImBF 4 follows a similar trend as from the aqueous and organic electrolyte solutions. The adsorption activity of anions increases in order Cl − < Br − < I − , despite the fact that the solvation properties of relevant media are significantly different. We discuss this trend in the light of a possible application of the RTIL mixtures as an electrolyte for electrochemical energy storage devices like supercapacitors. The ionic liquids as electrolytes have been studied since the early 20 th century, but there is still much to be understood regarding some fundamental aspects. [1][2][3][4][5][6] Theoretical models that explain the dependence of the differential capacitance values on the electrode potentials have been worked out for the aqueous and non-aqueous electrolytes and molten salts. 7,8 However, in the case of the specific adsorption, there are no detailed models for the electrical double layer capacitance, that analyze the influence of the surface-active anion concentration and electrode potential on the specific interaction energy (including charge transfer) and on the distance of the closest approach of anions onto the metal electrode surface.5,9,10 Therefore, the detailed analysis and characterization of these complex electrode | ionic liquid interfaces (with the addition of ions that might have strong chemical interactions and high interaction energies with electrode surface layer atoms, demonstrating very negative Gibbs adsorption energy values, so-called strong specific adsorption properties) is considered our high priority. Bismuth, as an electrode material, has been studied widely and has shown good electrochemical stability and high reproducibility of the data. The properties are inevitable for detailed investigation of interfacial adsorption and faradaic charge transfer processes. The amount of previously measured adsorption data from different electrolytes (including electrochemical impedance spectroscopy and in situ STM methods) enables to develop more realistic, i.e. complex models for the electrical double layer capacitance, that analyze the influence of the surface-active anion addition on the inner layer structure, dielectric permittivity, effective dipoles moment for dipole created at metal|RTIL interface, etc. 7,[11][12][13][14] To continue with the systematic research of halide ions, 1-ethyl-3-methylimidazolium bromide (EMImBr) was selected for the source of bromide ions. There are some theoretical and e...

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Molecular Dynamics of the Electrochemical Interface and the Double Layer

Groß

2021

Atomic‐Scale Modelling of Electrochemical Systems

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Halide adsorption on close-packed metal electrodes

Cited by 66 publications

References 31 publications

First-Principles Study of Chlorine Adsorption on Clean Al(111)

First-Principles Study of Chlorine Adsorption on Clean Al(111)

Electrochemical Investigation of 1-Ethyl-3-methylimidazolium Bromide and Tetrafluoroborate Mixture at Bi(111) Electrode Interface

Molecular Dynamics of the Electrochemical Interface and the Double Layer

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