Using electrochemical STM we studied monolayer high Au islands on Au(100) electrodes in sulfuric acid as a function of the electrode potential. We made use of theoretical and experimental methods recently developed for UHV experiments on metal islands. It is demonstrated that these models are likewise applicable to islands on metal electrodes in a liquid environment. From a quantitative analysis of the equilibrium island shape and of the island shape fluctuations we determined the step free energy (line tension) as a function of orientation and the kink energy, and the dependence of these quantities on the electrode potential. In a first approach to a theoretical understanding the electrostatic contributions to the line tension are considered. It is concluded that these contributions should add significantly to the observed variation with the potential. This fails however to provide essential features of the experimental result.
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http://dx.doi.org/10.1039/b110642m | DOI Listing |
Angew Chem Int Ed Engl
September 2024
Department of Chemistry-Ångström Laboratory, Uppsala University, Lägerhyddsvägen 1, BOX 538, 75121, Uppsala.
We have studied polarized Au(100) and Au(111) electrodes immersed in electrolyte solution by implementing finite-field methods in density functional theory-based molecular dynamics simulations. This allows us to directly compute the Helmholtz capacitance of electric double layer by including both electronic and ionic degrees of freedom, and the results turn out to be in excellent agreement with experiments. It is found that the electronic response of Au electrode makes a crucial contribution to the high Helmholtz capacitance and the instantaneous adsorption of Cl can lead to a charge inversion on the anodic polarized Au(100) surface.
View Article and Find Full Text PDFJ Chem Phys
June 2024
Department of Chemistry and Centre for Scientific Modeling and Computation, Chinese University of Hong Kong, Shatin, Hong Kong, China.
We report the free energy barriers for the elementary reactions in the 2e- and 4e- oxygen reduction reaction (ORR) steps on Au(100) in an alkaline solution. Due to the weak adsorption energy of O2 on Au(100), the barrier for the association channel is very low, and the 2e- pathway is clearly favored, while the barrier for the O-O dissociation channel is significantly higher at 0.5 eV.
View Article and Find Full Text PDFJ Chem Phys
June 2024
Department of Physics, Shanghai Key Laboratory of High Temperature Superconductors, International Centre of Quantum and Molecular Structures, Shanghai University, Shanghai 200444, China.
The orientation and rearrangement of water on a gold electrode significantly influences its physicochemical heterogeneous performance. Despite numerous experimental and theoretical studies aimed at uncovering the structural characteristics of interfacial water, the orientational behavior resulting from electrode-induced rearrangements remains a subject of ongoing debate. Here, we employed molecular dynamics simulations to investigate the adaptive structure and dynamics properties of interfacial water on Au(111) and Au(100) surfaces by considering a polarizable model for Au atoms in comparison with the non-polarizable model.
View Article and Find Full Text PDFJ Chem Phys
April 2024
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
In this work, we propose and validate a generalization of the Helmholtz model that can account for both "bell-shaped" and "camel-shaped" differential capacitance profiles of concentrated electrolytes, the latter being characteristic of ionic liquids. The generalization is based on introducing voltage dependence of both the dielectric constant "ϵr(V)" and thickness "L(V)" of the inner Helmholtz layer, as validated by molecular dynamics (MD) simulations. We utilize MD simulations to study the capacitance profiles of three different electrochemical interfaces: (1) graphite/[BMIm+][BF4-] ionic liquid interface; (2) Au(100)/[BMIm+][BF4-] ionic liquid interface; (3) Au(100)/1M [Na+][Cl-] aqueous interface.
View Article and Find Full Text PDFJ Phys Chem Lett
October 2022
Department of Chemistry and Centre for Scientific Modeling and Computation, Chinese University of Hong Kong, Shatin 999077, Hong Kong, China.
Using ab initio molecular dynamics simulations with fully solvated ions, we demonstrate that solvated OH forms a stable hydrogen bond with Au(100). Unlike the hydrogen bond between HO and Au reported previously, which is more favorable for negatively charged Au, the OH···Au interaction is stabilized when a small positive charge is added to the metal slab. For electro-catalysis, this means that while OH···Au plays a significant role in the hydrogen evolution reaction, OH···Au could be a significant factor in the oxygen reduction reaction in alkaline media.
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