Search

An overview is given of selected theoretical, experimental and computer simulation research on thermodynamic modeling applied to the metal underpotential deposition. Focus is made mainly on the last 20 years. The upd -theory on planar surfaces is revisited and the thermodynamic framework is extended to consider underpotential deposition on nanoparticles and to include anion coadsorption, solvation and double layer charging. Results from molecular dynamics and Monte Carlo simulations are shown for systems of experimental interest. At the end some perspectives for further advanced modeling of the present problem are given. [ABSTRACT FROM AUTHOR]

Abstract: The electrochemical decoration of Au and Pd nanoparticles by Pd and Au atoms respectively is discussed in a statistical mechanical framework. It is found that depending on precursor nanoparticle size and shape, controlled decoration may be achieved in undersaturation or oversaturation conditions. Multilayer deposition is also considered, with the finding that this phenomenon is also size dependent. [Copyright &y& Elsevier]

Abstract: A thermodynamic model predicting the disappearance of the underpotential deposition phenomenon in the limit of small nanoparticles is proposed and developed for selected families of geometric bodies. The key parameters are the binding energy of adatoms on the flat foreign substrate and at the edges of the nanoparticle. [Copyright &y& Elsevier]

Abstract: The meaning of underpotential shift is discussed for free nanoparticles, where a redox couple is used to set potential control on them. Atomistic Monte Carlo simulations are performed to study their decoration in the submonolayer regime. The resulting configurations are used to simulate their plasmon spectra by means of a state-of-the art quantum mechanical atomistic model. [Copyright &y& Elsevier]

Abstract: In the present work we discuss the statistical mechanical framework for predicting the decoration of metallic nanoparticles using electrochemical methods, in thermodynamic equilibrium. It is found that depending on the interactions between the two metals, controlled decoration may be achieved for core–shell nanoparticles in undersaturation and oversaturation conditions. The concept of underpotential deposition is discussed for the case of nanoparticles, with the finding that this phenomenon may be size dependent. [ABSTRACT FROM AUTHOR]