Chlorine‐Enhanced Surface Mobility of Au(100)

Abstract

Motivated by experimental studies of two-dimensional Ostwald ripening on Au(100) electrodes in chlorine-containing electrolytes, we have studied diffusion processes using density functional theory. We find that chlorine has a propensity to temporary form AuCl complexes, which diffuse significantly faster than gold adatoms. With and without chlorine, the lowest activation energy is found for the exchange mechanism. Chlorine furthermore reduces the activation energy for the detachment from kink sites. Kinetic Monte Carlo simulations were performed on the basis of extensive density functional theory calculations. The island-decay rate obtained from these Monte Carlo simulations, as well as the decay rate obtained from the theoretical activation energies and frequency factors when inserted into analytical solutions for Ostwald ripening, are in agreement with experimental island-decay rates in chlorine-containing electrolytes.

Anisotropic Mg Electrodeposition and Alloying with Ag-based Anodes from Non-Coordinating Mixed-Metal Borohydride Electrolytes for Mg Hybrid Batteries

“…Our previous results and those of Matsui show a {0001} 295 orientation when depositing Mg from a Grignard solution [1,5]. Schmickler has shown via DFT 296 calculations that Au-Cl complexes diffuse much faster than Au adatoms alone [37]. The change undetermined and future studies, both in experiment and theory, will be needed to address these issues.…”

Electrochemically Induced Ostwald Ripening in Au/TiO2 Nanocomposite

“…We believe that differences in the lattice energy and surface potentials χ (due to surface dipoles) of nanometals of different modifications should also be taken into account . The dependence of surface stability and the dynamics of surface structures on potential have already been studied for the two-dimensional Ostwald ripening of metal surfaces, on which large islands of one layer height grow at the expense of smaller ones . Two atomic processes were found to be rate-determining in this reformation: the detachment from a kink site and atomic diffusion on flat surfaces between the islands.…”

On the Energetics of Ions in Carbon and Gold Nanotubes

“…The difference in energy between the position at the center and the adsorption site is about 0.7 eV.T his strong bond weakens the gold-gold interaction and leads to as mall deformation of the gold tube (see Figure 7). This is reminiscent of the enhancement of gold adatomd iffusion by adsorbed chlorine, [28] which is also caused by the weakening of the gold-gold interaction. …”