Sulfur−Substrate Interactions in Spontaneously Formed Sulfur Adlayers on Au(111)

Vericat, Carolina; Vela, M. E.; Andreasen, and G.; Salvarezza, Roberto Carlos; and, L. Vázquez; Martín‐Gago, José A.

doi:10.1021/la0018179

Cited by 112 publications

(163 citation statements)

References 25 publications

(75 reference statements)

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“…Further annealing at 450 K results in ordering of the ring-like structure to reveal a quasirectangular unit cell with lattice parameters of 8.8 · 8.2 Å 2 . This ordered AuS phase seems to be a favorable configuration as very similar sulfur-induced surface structures on Au(111) have been prepared by electrooxidation in aqueous solutions of Na 2 S or H 2 S at room temperature, even though the interpretation of this structure is controversial [27,44,45]. Although most authors have suggested a model of adsorbed S 8 molecules, the sulfur-induced mobilization of Au atoms revealed in the present study clearly rules out a simple sulfur adlayer structure.…”

Section: Interaction Of Sulfur and Oxygen With Au(111) At High Coveragessupporting

confidence: 60%

“…Interestingly, in spite of the inert nature of Au with respect to gas molecules, sulfur has a relatively strong affinity for the gold surface. As such, gold surfaces are frequently used as models to investigate the adsorption of sulfur in electrochemical studies and as templates for synthesizing self-assembled monolayers of sulfur-containing organic molecules, such as alkanethiols [25][26][27]. These compounds undergo S-H bond cleavage and bind to the gold substrate via the sulfur.…”

Section: Introduction and Overviewmentioning

confidence: 99%

“…In particular, morphological changes during formation of self-assembled monolayers (SAMs) that limit edge definition in soft lithography are not well understood. Many models have been proposed based on the assumption that the Au atoms are unperturbed during sulfur adsorption [23,27,28]. However, as mentioned earlier, it may be important to consider that Au atoms released from Au surface are possibly involved in the interaction with sulfur atoms.…”

Section: Introduction and Overviewmentioning

confidence: 99%

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Reaction of Au(111) with Sulfur and Oxygen: Scanning Tunneling Microscopic Study

et al. 2005

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The reaction of sulfur and oxygen with the gold surface is important in many technological applications, including heterogeneous catalysis, corrosion, and chemical sensors. We have studied reactions on Au(111) using scanning tunneling microscopy (STM) in order to better understand the surface structure and the origin of gold's catalytic activity. We find that the Au(111) surface dynamically restructures during deposition of sulfur and oxygen and that these changes in structure promote the reactivity of Au with respect to SO 2 and O 2 dissociation. Specifically, the Au(111) herringbone reconstruction lifts when either S or O is deposited on the surface. We attribute this structural change to the reduction of tensile surface stress via charge redistribution by these electronegative adsorbates. This lifting of the reconstruction was accompanied by the release of gold atoms from the herringbone structure. At high coverage, clusters of gold sulfides or gold oxides form by abstraction of gold atoms from regular terrace sites of the surface. Concomitant with the restructuring is the release of gold atoms from the herringbone structure to produce a higher density of low-coordinated Au sites by forming serrated step edges or small gold islands. These undercoordinated Au atoms may play an essential role in the enhancement of catalytic activity of gold in reactions such as oxygen dissociation or SO 2 decomposition. Our results further elucidate the interaction between sulfur and oxygen and the Au(111) surface and indicate that the reactivity of Au nanoclusters on reducible metal oxides is probably related to the facile release of Au from the edges of these small islands. Our results provide insight into the sintering mechanism which leads to deactivation of Au nanoclusters and into the fundamental limitation in the edge definition in soft lithography using thiol-based self-assembled monolayers (SAMs) on Au. Furthermore, the enhanced reactivity of Au after release of undercoordinated atoms from the surface indicate a relatively insignificant role of an oxide support for high reactivity.

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Section: Interaction Of Sulfur and Oxygen With Au(111) At High Coveragessupporting

confidence: 60%

Section: Introduction and Overviewmentioning

confidence: 99%

Section: Introduction and Overviewmentioning

confidence: 99%

See 1 more Smart Citation

Reaction of Au(111) with Sulfur and Oxygen: Scanning Tunneling Microscopic Study

et al. 2005

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“…Rodriguez et al have studied the adsorption of sulfur on Au(111) with photoemission spectroscopy over a wide range of coverages (125). Supporting DFT calculations confirmed earlier findings by Gottschlack and Hammer (126) that sulfur preferred the three-fold hollow site at low coverages and induced a reconstruction to a √3 x √3 R30° pattern as seen by LEED (127). As the coverage was increased beyond ~0 .35 ML, the LEED pattern vanished and a reduction in the strength of Au-S bonds, accompanied by the formation of S2 species, was observed.…”

Section: 2supporting

confidence: 59%

Surface chemistry of catalysis by gold

et al. 2004

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IntroductionGold has long been regarded as an "inert" surface and bulk gold surfaces do not chemisorb many molecules easily. However, in the last decade, largely through the efforts of Masatake Haruta, gold particles, particularly those below 5 nm in size, have begun to garner attention for unique catalytic properties (1-8). In recent years, supported gold particles have been shown to be effective as catalysts for low temperature CO oxidation (9), selective oxidation of propene to propene oxide (10), water gas shift (11), NO reduction (12), selective hydrogenation of acetylene (or butadiene) (13)

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“…We addressed the occurrence of bright spots situated close to the step -DE molecule. Further, the value of the apparent height and the diameter of the bright spots can be attributed to the features of the 2S-avy debate whether it is the methyl tail group [15,16] or the S head group [17][18][19] that is observed as bright spots in the STM image. Our analysis does not depend on solving this puzzle by assuming that the alkane chains tilt uniformly covering the surface of the gold.…”

Section: Spectroscopic Contrast Of Diarylethene Molecules Onmentioning

confidence: 99%

Spectroscopic Contrast of Diarylethene Molecules on Octanethiol Monolayer

Arramel

Kudernác

Katsonis

et al. 2017

MST

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We present a systematic scanning tunneling microscopy (STM) study of bias-dependent imaging of disulfur diarylethene (2S-DE) molecules on octanethiol (C8) monolayer at room temperature. In a rigid confinement of the C8 matrix, we did not observe any significant variation in the appearance of the 2S-DE. On the contrary, a reversal in the apparent height of the 2S-DE was present when the molecule was situated on a gold vacancy island. We attributed this finding to the presence of a new electronic state that became accessible for a tunneling event. In addition, the C8 surface structure underwent a reversible phase transformation from √3 x √3 R30º hexagonal to c(4x2) square superlattice when the bias voltage was reduced from -825 mV to -425 mV or vice versa. Under a finite bias voltage, an appreciable topographic variation of the 2S-DE signature was demonstrated for the first time. This finding can be ascribed to a finite overlap of the associated wave functions that occurred between the tip state and the 2S-DE molecular energy level. We believe that physical insight on the bias-dependent imaging of organic molecules on solid surface is important towards the advancement of molecular electronics-based devices. AbstrakKontras Spektroskopi Molekul Diarylethene pada Monolayer Octanethiol. Makalah ini berisi hasil kajian sistematis yang telah dilakukan dengan menggunakan mikroskop penerowongan payaran (scanning tunneling microscopy (STM)) untuk mengamati perubahan prilaku molekul disulfurdiarylethene (2S-DE) pada molekul monolayer octanethiol (C8) di suhu ruangan, tergantung pada parameter tertentu. Pengamatan atas molekul 2S-DE yang terletak di daerah kekosongan substrat emas tidak menunjukkan adanya perubahan signifikan atas bentuk molekul 2S-DE, yang kemungkinan disebabkan oleh keberadaan fasa elektronik yang memungkinkan terjadinya fenomena tunneling. Struktur topografi dari matriks molekul penyusun (C8) juga mengalami perubahan transformasi fasa dari bentuk heksagonal √3 x √3 R30º menjadi square superlattice c(4x2) jika parameter pengukuran voltase untuk STM diubah dari -825 mV menjadi -425 mV ataupun sebaliknya. Perubahan yang terlihat pada bentuk fasa molekul 2S-DE terjadi pada rentang paratemer yang terbatas. Hasil pengamatan ini dapat dijelaskan sebagai hasil dari tumpangsuh yang terjadi antara fungsi gelombang tip state dan tingkat energi molekular dari 2S-DE. Hasil penelitian ini bermanfaat untuk memahami ketergantungan prilaku molekul organik di atas permukaan padat dalam rangka pengembangan perangkat berbasis elektronik molekular.

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Sulfur−Substrate Interactions in Spontaneously Formed Sulfur Adlayers on Au(111)

Cited by 112 publications

References 25 publications

Reaction of Au(111) with Sulfur and Oxygen: Scanning Tunneling Microscopic Study

Reaction of Au(111) with Sulfur and Oxygen: Scanning Tunneling Microscopic Study

Surface chemistry of catalysis by gold

Spectroscopic Contrast of Diarylethene Molecules on Octanethiol Monolayer

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