Underpotential deposition of copper and silver on single crystal surfaces of rhodium

Anjos, Daniela M.; Rigsby, Matthew A.; Wiȩckowski, Andrzej

doi:10.1016/j.jelechem.2009.10.003

Cited by 8 publications

(14 citation statements)

References 68 publications

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“…was reported by these authors [23]. Furthermore, X--ray photoelectron spectroscopy (XPS) of the surface after emersion of the electrode at potentials negative from this pre--peak confirmed the presence of copper on the surface.…”

Section: Discussionsupporting

confidence: 67%

Copper underpotential deposition on boron nitride nanomesh

Mertens

2017

Electrochimica Acta

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The boron nitride nanomesh is a corrugated monolayer of hexagonal boron nitride (h--BN) on Rh(111), which so far has been studied mostly under ultrahigh vacuum conditions. Here, we investigate how copper underpotential deposition (upd) can be used to quantify defects in the boron nitride monolayer and to assess the potential window of the nanomesh, which is important to explore its functionality under ambient and electrochemical conditions. In dilute sulfuric acid, the potential window of h--BN/Rh(111) is close to 1 volt, i.e. larger than that of the Rh substrate, and is limited by molecular hydrogen evolution on the negative and by oxidative removal on the positive side. From copper upd on pristine h--BN/Rh(111) wafer samples, we estimate a collective defect fraction on the order of 0.08-0.7% of the geometric area, which may arise from line and point defects in the h--BN layer that are created during its chemical vapour deposition. Overpotential deposition (opd) is demonstrated to have significant consequences on the defect area. We hypothesise that this non--innocent Cu electrodeposition involves intercalation originating at initial defects, causing irreversible delamination of the h--BN layer; this effect may be used for 2D material nanoengineering. On the relevant timescale, upd itself does not alter the defect area on repeated cycling; therefore, metal upd may find use as a general tool to determine the collective defect area in hybrids between 2D materials and various substrate metals.

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Section: Discussionsupporting

confidence: 67%

Copper underpotential deposition on boron nitride nanomesh

Mertens

2017

Electrochimica Acta

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“…As shown in previous work, the voltammetry of Rh(111) in the presence of copper ions presents two peaks in the region of potential before UPD, and the peaks are affected in intensity and position by the electrolyte used (22). This suggests that the interaction of anions with the rhodium surface plays a role in the UPD process.…”

Section: Resultssupporting

confidence: 55%

“…Underpotential deposition of Ag on Rh (111) As discussed in Anjos et al, silver UPD on Rh(111) in the presence of perchloric or sulfuric acid has distinctly different characteristics from copper UPD on Rh(111) (22). The cyclic voltammogram of silver UPD shows a multipeak feature, which is highly dependent on the type of the electrolyte in case, the concentration of silver ions in solution, and the ordering of the substrate surface.…”

Section: Resultsmentioning

confidence: 98%

Binding Energy Shifts for Cu and Ag UPD on Rh(111) Determined by Online EC-XPS

2010

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The nature of Cu and Ag underpotentially-deposited on Rh(111) was investigated by X-ray photoelectron spectroscopy (XPS). These underpotential deposition (UPD) systems present multipeak features, which were evaluated by cyclic voltammetry and in terms of binding energy shifts. The use of different electrolytes (sulfuric and perchloric acid) strongly affected the metallic coverage and slightly affected the UPD shifts. Through XPS, the examined surfaces were found to contain C, O, and S or Cl, which confirms the presence of anions and/or products of their reduction at the Rh (111) surface, in addition to the deposited metals. The binding energies for underpotentially-deposited Cu and Ag displayed negative shifts (to lower binding energy) with respect to both the bulk deposits and clean metal references. These negative shifts were discussed in terms of contributions from charge transfer, orbital rehybridization, and lattice strain.

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“…It could be due to the partially irreversible oxidation of Rh at higher pH. Such an irreversibility is usually also related to a competition of adsorbed hydrogen with adsorbed anions [27]. Furthermore, the 3D growth of Rh can produce nanostructures showing high index orientation [28], which causes complex adsorption processes.…”

Section: Resultsmentioning

confidence: 99%

Key role of anions in the 2D–3D electrochemical deposition of Rh on Ag electrodes

Schulz

Ruderman

Soldano

et al. 2015

Electrochimica Acta

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We have studied the electrochemical deposition of Rh on polycrystalline Ag substrates from electrolytes containing chloride and sulphate anions. Chronoamperometry and cyclic voltammetry have been employed in order to elucidate the growth mechanism. Anions play a key role in the growth mechanism and the resulting structures. In the presence of sulphate anions Rh deposition follows a 3D nucleationgrowth mechanism, while a 2D nucleation-growth is obeyed in the case of electrolytes containing chloride anions. Ab initio thermodynamics studies support the hypothesis that chloride anions stabilize the Rh deposition favouring a 2D mechanism at low overpotentials in good agreements with the experimental data. 2015 Published by Elsevier Ltd.

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Underpotential deposition of copper and silver on single crystal surfaces of rhodium

Cited by 8 publications

References 68 publications

Copper underpotential deposition on boron nitride nanomesh

Copper underpotential deposition on boron nitride nanomesh

Binding Energy Shifts for Cu and Ag UPD on Rh(111) Determined by Online EC-XPS

Key role of anions in the 2D–3D electrochemical deposition of Rh on Ag electrodes

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