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1.
J Phys Chem C Nanomater Interfaces ; 121(21): 11407-11415, 2017 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-28603579

RESUMO

Using a home-built reflectometer, we have investigated the changes in the optical reflectivity of a Pd(100) model catalyst during CO oxidation under high-pressure, high-temperature conditions. We observe changes in optical contrast when exposing the surface to CO oxidation conditions at 200 mbar from room temperature up to 400 °C. These changes in reflectivity are a result both of the formation of a surface oxide layer and of a change in surface roughness because of gas exposure. However, the reflectivity is more sensitive to the presence of a thin, flat oxide layer than to surface roughness. CO oxidation plays an important role in the decrease of the reflectivity. Since adding a reducing agent to the gas mixture renders it unlikely that the oxide thickness increases, we conclude that the observed decrease in reflectivity is dominated by increased surface roughness because of the catalytic reaction. We contribute this observed surface roughening to a Mars-van Krevelen-type reaction mechanism.

2.
Rev Sci Instrum ; 88(2): 023704, 2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-28249468

RESUMO

We have developed an experimental setup for optically monitoring a catalytically active surface under reaction conditions. A flow reactor with optical access allows us to image the behavior of an active catalyst surface down to the millimeter length scale. We use reflectance difference measurements with 625 nm light to investigate CO oxidation on Pd(100) at 300 mbar and 320 °C. We conclude that the changes in visible contrast result from the formation of an oxide layer after surface oxidation.

3.
Langmuir ; 28(40): 14143-54, 2012 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-22967093

RESUMO

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.

4.
Phys Chem Chem Phys ; 14(30): 10579-88, 2012 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-22751488

RESUMO

The electrochemical formation and dissolution of a lead/copper surface alloy on Cu(100) in chloride-containing electrolyte solutions were studied on the atomic scale by in situ scanning tunneling microscopy with high temporal and spatial resolution. Alloy formation, induced by a negative potential sweep, starts predominantly at the Cu steps, followed by the formation of a novel transient (4 × 3) alloy phase with 0.25 ML Pb coverage, which continuously is transformed into the 0.375 ML coverage c(4 × 4) phase, observed under UHV conditions. Both of these phases consist of rows of Pb atoms embedded into the Cu surface and exhibit highly dynamic structural fluctuations on sub 100 ms time scales. Upon increasing the potential again, a second c(4 × 4) phase with a different appearance in the STM images forms, which is attributed to partial dealloying, involving desorption of Pb from energetically less favorable sites. Further dealloying results in the formation of ribbon-like structures, already reported in previous studies. These ribbons are shown to consist of Pb atoms decorating domain boundaries in the c(2 × 2) chloride adlayer, left behind on the Cu surface by the dissolving surface alloy phase. Furthermore, dynamic observations of the subsequent coarsening of the ribbon network and the attachment/detachment of isolated Pd adsorbates to the ribbons are presented. Both isolated Pb adsorbates and Pb atoms in the ribbons are proposed to be stabilized by coadsorbed Cl.

6.
Phys Chem Chem Phys ; 12(42): 13992-8, 2010 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-20871873

RESUMO

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.

7.
Chemphyschem ; 11(7): 1438-45, 2010 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-20301174

RESUMO

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.

8.
J Am Chem Soc ; 131(30): 10362-3, 2009 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-19588964

RESUMO

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.

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