Nanoscale heterogeneity at the aqueous electrolyte-electrode interface

Abstract

Using molecular dynamics simulations, we reveal emergent properties of hydrated electrode interfaces that while molecular in origin are integral to the behavior of the system across long times scales and large length scales. Specifically, we describe the impact of a disordered and slowly evolving adsorbed layer of water on the molecular structure and dynamics of the electrolyte solution adjacent to it. Generically, we find that densities and mobilities of both water and dissolved ions are spatially heterogeneous in the plane parallel to the electrode over nanosecond timescales. These and other recent results are analyzed in the context of available experimental literature from surface science and electrochemistry. We speculate on the implications of this emerging microscopic picture on the catalytic proficiency of hydrated electrodes, offering an new direction for study in heterogeneous catalysis at the nanoscale.

8 pages, 5 figures

References in corpus (5)

• Testing Mode-Coupling Theory for a Supercooled Binary Lennard-Jones Mixture I: The van Hove Correlation Function
• A molecular perspective of water at metal interfaces
• Solvation at Aqueous Metal Electrodes
• Charge fluctuations in nano-scale capacitors
• Characterizing heterogeneous dynamics at hydrated electrode surfaces

Cited by in corpus (6)

• Molecular Simulation of Electrode-Solution Interfaces
• Use the force! Reduced variance estimators for densities, radial distribution functions and local mobilities in molecular simulations
• Mass-zero constrained molecular dynamics for electrode charges in simulations of electrochemical systems
• How do interfaces alter the dynamics of supercooled water?
• Rate constants in spatially inhomogeneous systems
• Exponential Scaling of Water Exchange Rates with Ion Interaction Strength from the Perspective of Dynamic Facilitation Theory