Dynamics of potential‐induced structural changes at the Ag(111)/alkaline interface

Abstract

The dynamics of the structural changes in the electrochemical double layer at the interface between a Ag(111) electrode and 0.1 M KOH electrolyte have been probed using surface X‐ray diffraction measurements. The X‐ray measurements utilised a lock‐in amplifier technique to obtain a time resolution down to the millisecond scale. Two potential step regions were explored in an attempt to separate the dynamics of the reversible adsorption/desorption of hydroxide species (OHad) and the subsequent cation (K+) ordering in the double layer. By probing different positions in reciprocal space, sensitive to different structural changes, the time‐dependent response of the electrode surface was probed and time constants for the different associated processes were obtained.

Structure of the Electrochemical Interface: Ag(hkl) in an Alkaline Electrolyte

“…The hysteresis observed in each XRV measurement is indicative of the relatively slow kinetics of the structural rearrangements of the entire electrochemical interface. X-ray measurements probing the kinetics of the structural rearrangements of Ag(111) in 0.1 M KOH have recently been published …”

“…X-ray measurements probing the kinetics of the structural rearrangements of Ag(111) in 0.1 M KOH have recently been published. 64 Following XRV measurements, CTR measurements on each surface were made to characterize the interface structures at the cathodic and anodic potential limits. The nonspecular CTR data are sensitive to the termination of the Ag crystal lattice and any chemisorbed species with well-defined bonding sites.…”