Abstract
Thermodynamic analysis and molecular dynamics simulations were conducted to systematically study the size-dependent electrochemical response of solids. By combining the generalized Young-Laplace equation with the popular Butler-Volmer formulation, the direct influence of surface stress on solid film electrochemical reactions was isolated. A series of thermodynamic formulas were developed to describe the size-dependent electrochemical properties of the solid surface. These formulas include intrinsic surface elastic parameters, such as surface eigenstress and surface elastic modulus. Metallic films of Au, Pt, Ni, Cu and Fe were studied as examples. The anodic current density of the metal film increased, while the equilibrium potential decreased with increasing solid film thickness.
Highlights
Thermodynamic analysis and molecular dynamics simulations were conducted to systematically study the size-dependent electrochemical response of solids
The present study focuses on the fundamental elastic properties of a solid surface and considers solid films as typical structures to simplify the theoretical analysis
In the sharp surface approach, a single dividing interface of zero thickness35 is used to separate a studied system from its environment and the surface contribution to the thermodynamic properties is defined as the excess over the values that would obtain if the studied system and environment retained their properties constant up to the dividing interface
Summary
Thermodynamic analysis and molecular dynamics simulations were conducted to systematically study the size-dependent electrochemical response of solids. Intrinsic surface elastic parameters were incorporated to reveal the physical origin of the size-dependent electrochemical corrosion properties, such as the current density of the electrode reactions, along with the equilibrium potentials of solid films. We assume that the surface thickness is 1 nm to study the size-dependent electrochemical properties of the solid films.
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