New insight on the behavior of the irreversible adsorption and underpotential deposition of thallium on platinum (111) and vicinal surfaces in acid electrolytes

Abstract

Please cite this article as: P.Rodriguez, N.García-Aráez, E.Herrero, J.M.Feliu, New insight on the behaviour of the irreversible adsorption and underpotential deposition of thallium on platinum (111) and vicinal surfaces in acid electrolytes, Electrochimica Acta http://dx.doi.org/10.1016/j.electacta. 2014.11.019 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. 1New insight on the behaviour of the irreversible adsorption and underpotential deposition of thallium on platinum (111) AbstractWe report, for the first time, the electrochemical behaviour of thallium irreversibly adsorbed on Pt (111) and platinum stepped surfaces composed of (111) terraces and monoatomic steps. Similar to the case of thallium UPD, the voltammograms obtained after thallium irreversible adsorption present three characteristic features. After a careful analysis of the effect of the thallium concentration, the concentration and nature of the anion of the supporting electrolyte and the pH of the solution on these voltammetric features, we have been able to ascribe these processes to Tl/Tl + oxidation and anion adsorption on the Tlmodified surface. In addition, the results obtained with stepped surfaces, indicate that some of the features are clearly associated to the presence of (111) surface domains, and thus they could be used for the quantification of these sites.

Probing the Surface of Noble Metals Electrochemically by Underpotential Deposition of Transition Metals

“…Therefore, upd of a metal monolayer onto polycrystalline or single-crystal substrates of a foreign metal has been studied intensively. These investigations included various substrates such as Au, Pt, Ag, Cu, Rh, Ru, Pd, and many deposited ions like Ag + [13,14], Cu 2+ [15][16][17][18][19][20][21][22][23][24], Cd 2+ [25], Pb 2+ [26][27][28][29][30], Tl + [31][32][33][34], Cd 2+ [35,36], Hg 2+ [37], Sn 2+ [38,39], Bi 3+ [30,[40][41][42][43][44][45], Ge 4+ [46][47][48], Sb 2+ [49][50][51], and Ni 2+ [52]. The charge corresponding to the upd permits researchers to estimate the amount of deposited metal.…”

Formic acid electrooxidation on thallium modified platinum single crystal electrodes

“…This result suggests that the peak at 0.48 V is related to the rearrangement of the sulfate layer adsorbed on the Tl modified Pt surface. The latter result was demonstrated by Rodriguez et al by the observation of the displacement of this peak when changing the sulfate concentration in the solution at a constant pH [18].…”

“…However, a new peak around 0.48 V appears very close to the spike in the unmodified surfaces. This sharp spike is related to the order disorder transition in the sulfate layer [17,18,24]. Thus, it can be proposed that Tl is modifying the energetics of this order-disorder transition.…”

“…In earlier studies, Clavilier et al [17] perfomed the underpotential deposition (UPD) of Tl + on Pt(111) electrode, arguing that there is an equilibrium in the adsorption-desorption process. More recently, Rodriguez et al [18] has studied extensively either the UPD and irreversible adsorption of Tl on…”

A comparison of the uniaxial deformation of copper and nickel (1 1 19) surfaces: a molecular dynamics study

“…It is clear that the displacement fields induced by these surface defects can profoundly affect the morphology of the surface. For example, in homo- or hetero-epitaxial growth, steps on a surface can act as nucleation centres or decrease the diffusion of adsorbed species due to the Ehrlich–Schwoebel barrier; in catalytic reactions stepped surfaces often have a different catalytic activity to that of flat surfaces 2 3 4 5 6 7 . Controlled deformation also appears to be a potential tool for the self-organization of surfaces, applicable in a bottom-up approach to the nanostructuring of materials.…”