Cu(111) in chloride containing acidic electrolytes: Coadsorption of an oxygenated species

Gründer, Yvonne; Drünkler, A.; Golks, Frederik; Wijts, G.; Stettner, J.; Zegenhagen, J.; Magnussen, Olaf M.

doi:10.1016/j.jelechem.2013.11.004

Cited by 10 publications

(17 citation statements)

References 38 publications

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“…In the case of copper, the surface has been shown to be in the metallic state in acidic solutions (pH < 5), 8,9 because of the fast dissolution of the oxide, and also in alkaline solutions in the underpotential range of Cu 2 O formation. This has been observed in 1 mM K 2 SO 4 alkaline solution of pH 8 or 10 at potential E < −0.90 V, 10 in 0.1 M NaOH solution of pH 13 at −0.675 ± 0.02 V/SHE, 11 and at potential E < −0.75 V. 12 Under these conditions, a theoretical model composed of a Cu(hkl) metal slab is appropriate to investigate adsorbate− copper interactions at the atomic scale.…”

Section: ■ Introductionmentioning

confidence: 99%

DFT-Based Cu(111)||Cu₂O(111) Model for Copper Metal Covered by Ultrathin Copper Oxide: Structure, Electronic Properties, and Reactivity

et al. 2020

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In many applications, metallic copper can be covered by an ultrathin native or a passive oxide film depending on the redox conditions of the interface formed with the environment, which governs its surface properties. In the present work, we constructed and optimized through quantum chemical DFT calculations a model of this Cu(111)||Cu 2 O(111) stoichiometric oxide supported in parallel epitaxy on Cu(111) substrate. Energetic analysis of the metal-oxide interface shows the stable formation of the interface between oxide film and metal substrate. The Cu 2 O(111) film binds to the Cu(111) surface via the unsaturated oxygen atoms bonded to copper metal atoms in top, bridge and hollow sites. Structural analysis of the Cu 2 O(111) film surface shows reconstruction with modifications of the distances between the unsaturated and the saturated copper atoms. The surface interlayer relaxation is inward for

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Section: ■ Introductionmentioning

confidence: 99%

DFT-Based Cu(111)||Cu₂O(111) Model for Copper Metal Covered by Ultrathin Copper Oxide: Structure, Electronic Properties, and Reactivity

et al. 2020

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“…It is believed that defects or an applied electrode potential may drive the substitution process, as verified by other DFT studies [6,46]. Moreover, competitive adsorption has been observed experimentally [4]. Obviously, more complicated models relevant for real metal surfaces are needed for further calculations.…”

Section: Resultsmentioning

confidence: 78%

“…The possibility of H 2 O dissociation on each investigated surface is discussed next. Since OH and Cl were reported experimentally to compete on metal surfaces [4], the substitution of OH by Cl is also discussed with respect to the mechanism of initiation of localized corrosion.…”

Section: Resultsmentioning

confidence: 99%

“…On one hand, Cl − ions are believed to damage metal surfaces and hinder the re-passivation of localized corrosion of metals [3,4,5,6]. In a previous work, we studied co-adsorption of Cl and O 2 molecules on an Al(111) surface by density functional theory (DFT) and found that the interaction of Cl and Al weakened the O–Al bond when the Cl/O ratio increased [5].…”

Section: Introductionmentioning

confidence: 99%

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Co-Adsorption of H2O, OH, and Cl on Aluminum and Intermetallic Surfaces and Its Effects on the Work Function Studied by DFT Calculations

et al. 2019

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The energetics of adsorption of H2O layers and H2O layers partially replaced with OH or Cl on an Al(111) surface and on selected surfaces of intermetallic phases, Mg2Si and Al2Cu, was studied by first-principle calculations using the density function theory (DFT). The results show that H2O molecules tended to bind to all investigated surfaces with an adsorption energy in a relatively narrow range, between –0.8 eV and –0.5 eV, at increased water coverage. This can be explained by the dominant role of networks of hydrogen bonds at higher H2O coverage. On the basis of the work function, the calculated Volta potential data suggest that both intermetallic phases became less noble than Al(111); also, the Volta potential difference was larger than 1 V when the coverage of the Cl-containing ad-layer reached one monolayer. The energetics of H2O dissociation and substitution by Cl as well as the corresponding work function of each surface were also calculated. The increase in the work function of the Al(111) surface was attributed to the oxidation effect during H2O adsorption, whereas the decrease of the work function for the Mg2Si(111)–Si surface upon H2O adsorption was explained by atomic and electronic rearrangements in the presence of H2O and Cl.

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“…Results from in situ electrochemical scanning tunneling microscopy (EC-STM) − and impedance spectroscopy, as presented in the following, indicate the complexity of the Cu(110) surface in hydrochloric acid (HCl) depending on the applied potentials. Possible reasons for misinterpretations arise from the high sensitivity of the surface to oxygen which will be considered in more detail in a subsequent publication. In ref , we have discussed by means of EC-STM the step-wise transformation of the Cu(110) surface from the pristine state, showing the 1 × 1 structure of the uppermost copper surface atoms, toward a faceted surface because of the increasing anodic potentials and chloride adsorption.…”

Section: Introductionmentioning

confidence: 99%

Chloride-Induced Surface States in Cu(110)/Liquid Interfaces

et al. 2020

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While surface states (SSs) have been widely exploited under ultrahigh vacuum conditions, their appearance and role in metal–electrolyte interfaces are still a controversial debate. The existence of SSs, similar to those shown here, permits control and tunability of electronic properties of functional metal–electrolyte interfaces. Resonant excitations among them could enhance, for example, photocatalytic reactions or permit further investigations of the surface chemistry of such reactions with surface resonance Raman spectroscopy. On the one hand, SSs and other properties are readily adjustable via an applied electrical potential, that is, by promoting changes in the chemical potential favoring adsorption of ionic species. On the other hand, the presence of the electrolyte induces additional scattering and screening effects, so that the electron charge distributions can differ considerably in the presence of high electric fields as compared to the respective surfaces in vacuum. Hence, a straightforward comparison is challenging. In this work, we report on a systematic study, by means of electrochemical impedance spectroscopy (EIS) jointly with in situ reflectance anisotropy spectroscopy (RAS), which aimed to assess the evolution of surface properties and SSs occurring at Cu(110) in contact with an HCl solution. Thereafter, by modeling the RAS response and in comparison with electrochemical scanning tunneling microscopy measurements, specific surface structures have been identified and ascribed to the optical response. In a specific potential range, three additional resonances are detected in RAS that can be explained by two-dimensional confined SSs. This work renders both in situ RAS and EIS as useful tools to study and tune SSs in a systematic way by applied electrical potentials, thereby stabilizing thermodynamically preferred surface structures.

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Cu(111) in chloride containing acidic electrolytes: Coadsorption of an oxygenated species

Cited by 10 publications

References 38 publications

DFT-Based Cu(111)||Cu₂O(111) Model for Copper Metal Covered by Ultrathin Copper Oxide: Structure, Electronic Properties, and Reactivity

DFT-Based Cu(111)||Cu₂O(111) Model for Copper Metal Covered by Ultrathin Copper Oxide: Structure, Electronic Properties, and Reactivity

Co-Adsorption of H2O, OH, and Cl on Aluminum and Intermetallic Surfaces and Its Effects on the Work Function Studied by DFT Calculations

Chloride-Induced Surface States in Cu(110)/Liquid Interfaces

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Cu(111) in chloride containing acidic electrolytes: Coadsorption of an oxygenated species

Cited by 10 publications

References 38 publications

DFT-Based Cu(111)||Cu2O(111) Model for Copper Metal Covered by Ultrathin Copper Oxide: Structure, Electronic Properties, and Reactivity

DFT-Based Cu(111)||Cu2O(111) Model for Copper Metal Covered by Ultrathin Copper Oxide: Structure, Electronic Properties, and Reactivity

Co-Adsorption of H2O, OH, and Cl on Aluminum and Intermetallic Surfaces and Its Effects on the Work Function Studied by DFT Calculations

Chloride-Induced Surface States in Cu(110)/Liquid Interfaces

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Product

Resources

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DFT-Based Cu(111)||Cu₂O(111) Model for Copper Metal Covered by Ultrathin Copper Oxide: Structure, Electronic Properties, and Reactivity

DFT-Based Cu(111)||Cu₂O(111) Model for Copper Metal Covered by Ultrathin Copper Oxide: Structure, Electronic Properties, and Reactivity