Direct Measurement of the Adsorption Kinetics of Alkanethiolate Self-Assembled Monolayers on a Microcrystalline Gold Surface

Karpovich, Dzmitry; Blanchard, G. J.

doi:10.1021/la00021a066

Cited by 462 publications

(549 citation statements)

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“…26,[30][31][32][33] The adsorption free energy obtained in this work is close to the value deduced from the infrared adsorption study of benzenedithiol onto a Ag film in benzene (−9.4 kcal/mol). The adsorption energy was found to widely vary: as small as ∼−5 kcal/mol for alkanethiols on a microcrystalline gold surface and ∼−20 kcal/mol for nalkanethiolates on Ag(111), and should be examined further.…”

supporting

confidence: 80%

Communication: Reactions and adsorption at the surface of silver nanoparticles probed by second harmonic generation

Gan

Gonella

Zhang

et al. 2011

The Journal of Chemical Physics

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supporting

confidence: 80%

Communication: Reactions and adsorption at the surface of silver nanoparticles probed by second harmonic generation

Gan

Gonella

Zhang

et al. 2011

The Journal of Chemical Physics

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“…21,22 On the other hand, it is almost two times greater than those reported for the adsorption of some alkanethiolates on gold. 23 This observation reflects the dependence of the surface-head group reaction on the electron density of the adsorbing sulfur. In fact, monolayers formed with inorganic complexes that enhance the electron density on the sulfur adsorbing atom, as consequence of a -back-bonding interaction, have shown to be more robust than their organic counterparts.…”

Section: Reductive Desorption Resultsmentioning

confidence: 85%

5-(4-pyridinyl)-1,3,4-oxadiazole-2-thiol on gold: SAM Formation and electroactivity

Paulo

Silva

Pinheiro

et al. 2008

J. Braz. Chem. Soc.

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O composto 5-(4-pyridinyl)-1,3,4-oxadiazole-2-thiol (Hpyt) adsorve espontaneamente sobre ouro formando SAMs ("Self-Assembled Monolayers") que, de acordo com os resultados eletroquímicos e de STM ("Scanning Tunneling Microscopy"), contêm poros através dos quais as moléculas dos complexos [Fe(CN) 6 ] 4-, a dependência da corrente faradáica com o pH da solução eletrolítica permitiu o cálculo do pKa da molécula de Hpyt adsorvida sobre ouro (4,2). Os parâmetros termodinâmicos, H ads and G ads , para o processo de adsorção desta molécula foram estimados em -20,01 e -39,39 kJ mol -1 , respectivamente, utilizando-se o modelo de Langmuir. O processo redox da metaloproteína citocromo c foi estudado utilizando-se a SAM de Hpyt. A constante de velocidade heterogênea de transferência de elétrons foi calculada em 2,29 10 -3 cm s -1 .5-(4-pyridinyl)-1,3,4-oxadiazole-2-thiol (Hpyt) spontaneously adsorbs on gold forming SAMs (self-assembled monolayers) that, based on STM (Scanning Tunneling Microscopy) and electrochemical data, contain pinholes through which [Fe(CN) 6 ] 4-and [Ru(NH 3 ) 6 ] 3+ probe molecules access the underlying gold electrode. For the former molecule, the dependence of the faradaic current on the electrolyte solution pH value allowed the evaluation of the surface pKa as 4.2. The thermodynamic parameters H ads and G ads for the Hpyt adsorption process could be described by the Langmuir model and were calculated as -20.01 and -39.39 kJ mol -1 , respectively. Electrodic redox reaction of cytochrome c metalloprotein was accessed by using the Hpyt SAM with a heterogeneous electron transfer rate constant of 2.29 10 -3 cm s -1 .

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“…The self-assembly is achieved by a chemical bond formation between the substrate atoms and sulfur atoms of the thiols and the hydrophobic interaction between the alkyl chains. The formation process and the structure of the thiol SAMs on Au(111) have been studied in detail by various techniques including IR [4,5], quartz crystal balance (QCM) [6,7] and scanning tunneling microscopy (STM) [8][9][10]. It is now well known that the alkanethiols are arranged in striped structures when the coverage is low [8][9][10] and in a (√3 x √3)R30° or c(4√3 x 2√3) structure with a tilt angle of 30° from the surface normal when the coverage becomes high [11].…”

Section: Introductionmentioning

confidence: 99%

Electrochemical oxidative adsorption and reductive desorption of a self-assembled monolayer of decanethiol on the Au(111) surface in KOH+ethanol solution

Sumi

Wano

Uosaki

2003

Journal of Electroanalytical Chemistry

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The electrochemical characteristics of an Au(111) electrode were investigated in 0.1 M KOH ethanol solutions containing various concentrations of decanethiol. Anodic and cathodic peaks corresponding to the oxidative adsorption and reductive desorption, respectively, of a self-assembled monolayer (SAM) of decanethiol were observed. Both peaks negatively shifted with the increase in the thiol concentration by ca. 57 mV/decade, showing that the redox process is a one-electron process. The adsorbed amount determined from the charge corresponding to the reductive desorption increased with an increase in the decanethiol concentration but never reached the saturated amount as long as the cyclic voltammograms were continuously recorded with the sweep rate of 10 -200 mV s-1. It increased with the holding time at +0.1 V, which was much more positive than the anodic peak potential, and reached the saturated amount in ca. 10 min in the 10 μM thiol solution. The reductive peak potential also negatively shifted with the holding time but for a longer period. It kept shifting for ca. 60 min in the 10 μM thiol solution, which is much longer than the time when the adsorbed amount reached the saturated value. These results suggest that the formation of a highly ordered SAM requires a much longer time than the adsorption of the thiol.2

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Direct Measurement of the Adsorption Kinetics of Alkanethiolate Self-Assembled Monolayers on a Microcrystalline Gold Surface

Cited by 462 publications

References 3 publications

Communication: Reactions and adsorption at the surface of silver nanoparticles probed by second harmonic generation

Communication: Reactions and adsorption at the surface of silver nanoparticles probed by second harmonic generation

5-(4-pyridinyl)-1,3,4-oxadiazole-2-thiol on gold: SAM Formation and electroactivity

Electrochemical oxidative adsorption and reductive desorption of a self-assembled monolayer of decanethiol on the Au(111) surface in KOH+ethanol solution

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