Electrochemical hydrogen evolution on (100)-oriented copper electrodes is shown to induce a novel surface reconstruction, which substantially influences the rates of this electrochemical reaction. As revealed by in situ video-STM the formation of this phase starts with lateral displacements of Cu surface atoms from lattice positions, resulting in stripe-like structures, followed by expansion of the surface lattice along the stripe direction.

The surface structure of Cu(100) electrodes in perchloric acid solutions of pH 1 to 3 was studied in the potential range of hydrogen evolution by video-rate scanning tunneling microscopy, focusing on the recently reported hydrogen-induced surface reconstruction [H. Matsushima et al., J. Am. Chem. Soc. 2009, 131, 10362]. Potential-dependent measurements reveal a two step formation process: at potentials close to the onset of hydrogen evolution a p(1×8) phase emerges, where Cu surface atoms in stripe-like structures are laterally and vertically displaced; at ≈30 mV more negative potentials a transition to a c(p×8) structure with an expanded Cu surface lattice occurs. Correlation of these observations with electrochemical data and studies on hydrogen interactions with Cu(100) surfaces under vacuum conditions support that these phases are induced by hydrogen in subsurface sites, pointing towards a high hydrogen coverage on this electrode surface under reaction conditions.

The interactions between adsorbates at a solid-liquid interface were studied by video-rate STM for the case of sulfur on Cu(100) electrode surfaces in HCl solution. Quantitative data were obtained by analyzing the S(ad) dimer dynamics within the surrounding c(2 x 2)-Cl adlattice as well as the adsorbate configurations. The interactions are repulsive for S(ad) separated by one or two lattice spacings and attractive at a separation of square root of 2 with energies comparable to adsorbates at the solid-vacuum interface. The S(ad) diffusion barriers are significantly reduced in the vicinity of a neighboring adsorbate.

The atomic-scale surface dynamic behavior of adsorbed methyl thiolate on Cu(100) electrodes, prepared via the dissociative adsorption of dimethyl disulfide, was studied in 0.01 M HCl solution over a wide regime of coverages. Using video-rate in situ STM, we directly observed the motion of the adsorbates within the c(2 × 2) lattice of the chloride coadsorbates with high spatial and temporal resolution, revealing complex mutual interactions of the organic adsorbates as well as pronounced interactions with Cu adatoms, which significantly affect the thiolate self-assembly. Quantitative measurements of the tracer diffusion of isolated thiolates reveal a 35 meV lower diffusion barrier as compared to that of sulfide adsorbates with a linear potential dependence of 0.5 eV/V. The effective intermolecular interactions between the thiolates resemble those between adsorbed sulfide and are repulsive at the nearest-neighbor distance of a(0) within the c(2 × 2) lattice, attractive at the next-nearest-neighbor distance of √2a(0) and again repulsive at a distance of 2a(0). Thiolates at these small spacings are found to exhibit characteristic collective properties, which are significant for the self-assembly of these species: First, their mobility is greatly enhanced relative to that of isolated thiolates. Second, Cu adatoms can be transiently trapped in between the two thiolates of a metastable dimer with an intermolecular spacing of √2a(0). With increasing coverage, small, highly mobile molecular clusters and subsequently the formation of ordered adlayer domains with a c(2 × 6) structure are observed. Common structural elements of the clusters and c(2 × 6) domains are stripes of thiolate dimers, which are oriented in the [011] direction, spaced at distances of √2a(0) and of which a large fraction is occupied by Cu adatoms. The c(2 × 6) phase can be rationalized as a close-packed arrangement of these dimer stripes. Because of the self-acceleration of the thiolate mobility, the ordering and reorganization of the ordered c(2 × 6) adlayers occur orders of magnitude faster than the surface diffusion of isolated thiolates, illustrating the importance of collective effects in organic self-organization.

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(2x2) lattice of coadsorbed chloride. S(ad) tracer diffusion occurs via hopping between neighboring c(2x2) 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 approximately 7 A. 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(2x2) domains. Attractive interactions between S(ad) and domain boundaries in the c(2x2) adlayer result in boundary pinning as well as transient trapping and enhanced diffusion of S(ad) along the boundary.