Adsorption of Dodecanethiol on Cu(110):  Structural Ordering upon Thiolate Formation

Kühnle, Angelika; Vollmer, S.; Linderoth, Trolle R.; Witte, Gregor; Wöll, Christof; Besenbacher, Flemming

doi:10.1021/la025661j

Cited by 37 publications

(36 citation statements)

References 28 publications

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“…The similarities of the decompositions behavior is inherent to the inability of the surfactant to contain the melted LiAlH4 and thus a loss of the nanosize feature in the favor of larger molten agglomerates behaving like bulk LiAlH4. The decomposition of the dodecanthiol as evidenced by mass spectrometry near 220 °C [35] further supports this hypothesis (Figure 3d). The fragments C3H5 + and C3H7 + correspond to the decomposition of the 1-dodecanethiol surfactant [36].…”

Section: Resultssupporting

confidence: 67%

Synthesis of LiAlH4 Nanoparticles Leading to a Single Hydrogen Release Step upon Ti Coating

Wang

Aguey‐Zinsou

2017

Inorganics

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Lithium aluminum hydride (LiAlH 4 ) is an interesting high capacity hydrogen storage material with fast hydrogen release kinetics when mechanically activated with additives. Herein, we report on a novel approach to produce nanoscale LiAlH 4 via a bottom-up synthesis. Upon further coating of these nanoparticles with Ti, the composite nanomaterial was found to decompose at 120 • C in one single and extremely sharp exothermic event with instant hydrogen release. This finding implies a significant thermodynamic alteration of the hydrogen properties of LiAlH 4 induced by the synergetic effects of the Ti catalytic coating and nanosizing effects. Ultimately, the decomposition path of LiAlH 4 was changed to LiAlH 4 → Al + LiH + 3/2H 2 .

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Section: Resultssupporting

confidence: 67%

Synthesis of LiAlH4 Nanoparticles Leading to a Single Hydrogen Release Step upon Ti Coating

Wang

Aguey‐Zinsou

2017

Inorganics

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“…Consequently, judicious engineering of the relation between the strength of the short-range attraction and the long-range repulsion allows tailoring of film patterns and pore sizes almost at will. Adsorbate films with tailored pores could serve as templates for the growth of nanoparticles at surfaces, providing homogeneous spatial and size distributions for catalytic, electronic, or mechanic applications, as well as for biocompatibility and the reduction of friction (16)(17)(18). …”

mentioning

confidence: 99%

A Homomolecular Porous Network at a Cu(111) Surface

Pawin

Wong

Kwon

et al. 2006

Science

268

230

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Anthraquinone molecules self-assemble on a Cu(111) surface into a large two-dimensional honeycomb network (square root of 304 x square root of 304)R23 degrees with pore diameters of approximately 50 A. The spontaneous formation of a pattern containing pores roughly five times larger than the size of the constituent molecules is unprecedented. The network originates from a delicate balance between substrate-mediated repulsion and intermolecular attraction involving an unusual chemical motif: hydrogen bonding between a carbonyl oxygen and an aromatic hydrogen atom. Substrate-mediated long-range adsorbate-adsorbate repulsion has been observed on anisotropic surfaces and in the context of the absence of pattern formation. Its applicability for the design of tailored molecular films is explored here.

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“…Vacuum deposition of thiols allows the study of low coverages, and a large variety of different alkanethiols patterns have been reported. [9][10][11][12] To the best knowledge of the authors, low coverages of arenethiols have not been addressed so far, although arenethiols have much larger potential for electronic applications than alkanethiols. This study uses thiophenol (TP) and…”

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confidence: 99%

Effect of Halo Substitution on the Geometry of Arenethiol Films on Cu(111)

et al. 2004

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Thiol films on noble metal surfaces attract considerable interest due to their ability of facile self-assembly from the solution phase. 1 Films of only monomolecular thickness can modify the electronic, physical, and chemical properties of the underlying substrate dramatically. This offers powerful opportunities for fundamental studies of electron transport, 2 single-molecule devices (e.g., tunneling diodes 3 or transistor 4 ), control of surface wettability, 5 etc. The formation of thiol films is driven predominantly by strong substrate-sulfur interactions. At saturation coverage, the result is a layer of molecules that stand close to upright on the surface. For alkanethiols on Au(111), ( 3 x 3)R30°and related superlattices were inferred. [6][7][8] In a solution environment, it is difficult to follow the initial stages of thiol chemisorption because of their high surface mobility prior to formation of a dense film and the presence of the surrounding solution. Vacuum deposition of thiols allows the study of low coverages, and a large variety of different alkanethiols patterns have been reported. [9][10][11][12] To the best knowledge of the authors, low coverages of arenethiols have not been addressed so far, although arenethiols have much larger potential for electronic applications than alkanethiols. This study uses thiophenol (TP) and, and pentafluoro-substituted (5FTP) analogues as model compounds for arenethiol film formation and explores the impact of a slight variation of arenethiol size and substituent electronegativity (EN) on the films' structural properties. We studied a broad range of coverages and found the most dramatic effects at incomplete films, where the molecules aggregate into isolated islands that are separated by empty terraces.We used two home-built STM systems that were operated in UHV (<10 -10 Torr) at cryogenic temperatures (15 or 81 K). Multiple cryopanels enclosed the STMs in order to minimize drift and sample contamination. We used a Cu(111) single crystal as a substrate. Sample preparation involved cycles of sputtering (Ar, 1.5 keV) and annealing (600 K). All arenethiol coverages were prepared by backfilling the chamber to a pressure of ∼10 -9 Torr and (if necessary, multiple cycles of) sample exposure for ∼15 s.We observed spontaneous formation of the superlattices in Figure 1 at 81K, which suggests that they may form transiently during the deposition of larger coverages. Figure 1a,b shows STM images of isolated CTP and TP molecules at 15 K after hydrogen abstraction. The molecules adsorb flat on the surface, and their image has a depression that we associate with the position of the thiol group. Using lateral manipulation 13 and coadsorption of CO for registry, 14 we find that both the S and the halogen atoms occupy Cu(111) hollow sites. The overall shape of FTP, 5FTP, and BTP is similar to Figure 1a,b and their size scales with the dimension of the substituent(s). Figure 1c-f shows a clean Cu(111) surface and islands of the parasubstituted molecules. Fourier transformation (FT) ...

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Adsorption of Dodecanethiol on Cu(110): Structural Ordering upon Thiolate Formation

Cited by 37 publications

References 28 publications

Synthesis of LiAlH4 Nanoparticles Leading to a Single Hydrogen Release Step upon Ti Coating

Synthesis of LiAlH4 Nanoparticles Leading to a Single Hydrogen Release Step upon Ti Coating

A Homomolecular Porous Network at a Cu(111) Surface

Effect of Halo Substitution on the Geometry of Arenethiol Films on Cu(111)

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