In Situ Video‐STM Studies of Adsorbate Dynamics at Electrochemical Interfaces

The dynamic behavior of individual adsorbates at electrochemical interfaces was studied directly by in situ high‐speed scanning tunneling microscopy, using sulfur adsorbed on Cu(100) electrodes in 0.01  M HCl solution as an example. By dosing from diluted Na 2 S solutions S ad coverages of a few percent can be prepared, with the sulfur adsorbates occupying positions within the c (2×2) lattice of coadsorbed chloride. S ad tracer diffusion occurs via hopping between neighboring c (2×2) lattice sites at considerably higher rates than those of sulfur on Cu(100) under UHV conditions, indicating a pronounced influence of the electrochemical environment on the adsorbate surface dynamics. The diffusion barrier linearly increases by 0.5 eV per V with potential and is strongly affected by neighboring S ad and surface defects. The S ad S ad interactions extend over ≈7 Å. They are repulsive between nearest‐neighbor and attractive between next‐nearest‐neighbor sites, respectively, and result in significantly reduced diffusion barriers. S ad on the upper terrace side of steps are transiently trapped and exhibit lower diffusion rates, leading to the formation of small metastable p (2×2) domains. Attractive interactions between S ad and domain boundaries in the c (2×2) adlayer result in boundary pinning as well as transient trapping and enhanced diffusion of S ad along the boundary.