Equilibrium coverage of halides on metal electrodes

Gossenberger, Florian; Roman, Tanglaw; Groß, Axel

doi:10.1016/j.susc.2014.01.021

Cited by 89 publications

(90 citation statements)

References 68 publications

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“…Furthermore, it should be noted that computational CVs are a less studied field, due to the difficulties of simulating the electrochemical interface, as compared to binding energy and other reactivity trend studies. Whereas, calculation of adsorbate coverages can be found in the literature …”

Section: Introductionmentioning

confidence: 99%

Ab Initio Cyclic Voltammetry on Cu(111), Cu(100) and Cu(110) in Acidic, Neutral and Alkaline Solutions

et al. 2019

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Electrochemical reactions depend on the electrochemical interface between the electrode surfaces and the electrolytes. To control and advance electrochemical reactions there is a need to develop realistic simulation models of the electrochemical interface to understand the interface from an atomistic point‐of‐view. Here we present a method for obtaining thermodynamic realistic interface structures, a procedure we use to derive specific coverages and to obtain ab initio simulated cyclic voltammograms. As a case study, the method and procedure is applied in a matrix study of three Cu facets in three different electrolytes. The results have been validated by direct comparison to experimental cyclic voltammograms. The alkaline (NaOH) cyclic voltammograms are described by H* and OH*, while in neutral medium (KHCO3) the CO3* species are dominating and in acidic (KCl) the Cl* species prevail. An almost one‐to‐one mapping is observed from simulation to experiments giving an atomistic understanding of the interface structure of the Cu facets. Atomistic understanding of the interface at relevant eletrolyte conditions will further allow realistic modelling of electrochemical reactions of importance for future eletrocatalytic studies.

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Section: Introductionmentioning

confidence: 99%

Ab Initio Cyclic Voltammetry on Cu(111), Cu(100) and Cu(110) in Acidic, Neutral and Alkaline Solutions

et al. 2019

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“…However, while traditional DFT does not provide a framework for addressing the free energy shifts as conditions in the experimental environment change, approximations and approaches for addressing these problems is an area of recent growth. [39][40][41][42][43] In these methods, different approximations are applied to model the half-cell. The Neurock group, 43 for instance, creates a half-cell in which the slab is at a fixed potential, and the cell is neutralized by an evenly-distributed background charge.…”

Section: Introductionmentioning

confidence: 99%

Formic acid oxidation on platinum: a simple mechanistic study

Schwarz

Sundararaman

Moffat

et al. 2015

Phys. Chem. Chem. Phys.

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The oxidation of small organic acids on noble metal surfaces under electrocatalytic conditions is important for the operation of fuel cells and is of scientific interest, but the basic reaction mechanisms continue to be a matter of debate. Formic acid oxidation on platinum is one of the simplest of these reactions, yet even this model system remains poorly understood. Historically, proposed mechanisms for the oxidation of formic acid involve the acid molecule as a reactant, but recent studies suggest that the formate anion is the reactant. Ab initio studies of this reaction do not address formate as a possible reactant, likely because of the difficulty of calculating a charged species near a charged solvated surface under potential control. Using the recently-developed joint density functional theory (JDFT) framework for electrochemistry, we perform ab initio calculations on a Pt(111) surface to explore this reaction and help resolve the debate. We find that when a formate anion approaches the platinum surface at typical operating voltages, with H pointing towards the surface, it reacts to form CO2 and adsorbed H with no barrier on a clean Pt surface. This mechanism leads to a reaction rate proportional to formate concentration and number of available platinum sites. Additionally, high coverages of adsorbates lead to large reaction barriers, and consequently, we expect the availability of metal sites to limit the experimentally observed reaction rate.

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“…We will first illustrate this approach with respect to the equilibrium coverage of halides on metal electrodes [30]. Electrochemistry is concerned with processes at the interface between an electron and an ion conductor [31], and in the case of an aqueous electrolyte the ion conductivity is mediated by solvated ions.…”

Section: Interfaces In Electrochemical Cellsmentioning

confidence: 99%