Oxygen Reduction on Amalgamated Platinum Electrodes Coated with Monolayers of Cetyl Alcohol and Stearic Acid

Oxygen reduction on an amalgamated platinum electrode with a monolayer of cetyl alcohol or stearic acid is studied. It is shown that the process proceeds inside the monolayer, most probably, at a certain distance from the metal; an electron is transferred to the reagent by the superexchange mechanism. The process characteristics depend on competition between several factors: the electron transfer distance, the potential drop between the electrode and the reagent in a given site in the monolayer, and the hydrogen ion concentration distribution across the film. The penetration of H⁺ inside the film appears to be responsive to the monolayer structure.     

Interfacial kinetic enhancement of metal ion adsorption on binary mixed self-assembled monolayers

The adsorption of metal ions, a type of surface reaction on binary mixed self-assembled monolayers (SAMs) on a gold surface composed of 1,6-hexanedithiol (HDT) with 11-mercaptoundecanoic acid (MUA), was monitored by in situ surface plasmon resonance (SPR) measurements. The differential SPR reflectance (ΔR) enables the kinetics of adsorption of Pt²⁺ on the mixed SAMs to be investigated. Unlike single HDT SAM, kinetic analyses of the mixed SAMs showed that the rate of adsorption of Pt²⁺ was enhanced and that it was highly dependent on the fraction of MUA present. These SPR measurements suggest that the adsorption rate of metal ions can be readily manipulated simply by using mixed SAMs.     

Structure and properties of 1,4-benzenedimethanethiol films grown from solution on Au(1 1 1): An XPS and NEXAFS study

Core level photoemission and X-ray absorption at the carbon C 1s edge are applied to the study of chemisorption of 1,4-benzenedimethanethiol molecules on Au(1 1 1) and to investigate the effect of the solvent used to prepare the organic films. 1,4-Benzenedimethanethiol films were prepared in polar and non-polar solvents, i.e. ethanol, methanol and n-hexane. 1,4-Benzenedimethanethiol molecules are anchored to the substrate through a single S-Au bond; the molecules in the films tend to assume an upright orientation, the aromatic ring resulting tilted towards the direction perpendicular to the substrate plane. The films present an effective thickness corresponding to more than a single layer. Only small differences are observed among behaviours in different solvents. It is concluded that the final properties and conformation of the 1,4-benzenedimethanethiol films are largely determined by the reciprocal interactions between the molecules and with the substrate.     

Thermal stability of alkoxy monolayers grafted on Si(1 1 1)

Direct grafting of organic monolayers on Si is of prime interest in order to give specific properties to a silicon surface. However, for microelectronics applications, this possibility is hampered by the limited stability of the grafted layers. It has been previously established that alkyl layers attached to Si surfaces through Si-C bonds become unstable at 250-300 °C, by desorption of alkenes. Changing the nature of the bonding to the surface might allow one to circumvent this desorption pathway and increase the layer stability. In our work, decanol and decyl aldehyde are reacted with the Si(1 1 1)-H surface at ∼100 °C during 20 h in order to obtain alkoxy monolayers. FTIR measurements performed in ATR geometry show that the grafted molecule surface coverage is on the order of 33% after reaction with decanol and 50% after reaction with decyl aldehyde. Characterization by AFM essentially reveals that the morphology of the grafted surfaces is unaffected as compared to that of Si-H surfaces. However, the edges of the terraces at alcohol-grafted surfaces exhibit some pitting, probably due to the presence of water in the grafting liquid. Thermal stability studies show that alkoxy chains progressively disappear from the Si surface between 200 and 400 °C. From the CH₂/CH₃ ratio in the CH region (2760-3070 cm⁻¹), it appears that the chains undergo progressive dissociation by C-C bond breaking before their complete disappearance from the surface. Therefore, the thermal behaviour of alkoxy monolayers appears quite distinct from that of alkyl monolayers that tend to leave the surface in a much narrower temperature range (250-350 °C), essentially via breaking of the Si-C bonds.     

导电分子巯基紫罗碱电子结构的理论计算

用密度泛函B3LYP/6-31G**计算方法,对不同碳链长度和不同氧化态( V2 +/V+.)紫罗碱二硫醇的平衡几何构型及相应电子结构的研究表明,两种氧化态在吡啶环共面性和前线轨道电子集居上的差异与特征,导致氧化态V2 +成为紫罗碱亲合金原子形成Au-S-nVn-S-Au结构的关键组分,自由基V+.则在该结构的氧化还原电子传导中发挥核心作用.S-S核间距与前线轨道能隙的计算结果表明,在紫罗碱二硫醇单分子电导的测量中,亚甲基数n达到12的分子长度是有效的.     

Anchoring of sulfur‐containing alkylphosphonic and semifluorinated alkylphosphonic molecules on a polycrystalline aluminum substrate

Self‐assembly on a polycrystalline aluminum substrate of two sulfur‐containing alkylphosphonic acids, CH₃? (CH₂)₁₁? S? (CH₂)₂? PO(OH)₂, and CF₃? (CF₂)₇? (CH₂)₂? S? (CH₂)₂? PO(OH)₂, has been compared with CH₃? (CH₂)₁₅? PO(OH)₂. The reaction of the phosphonic head groups with the hydroxyls at the alumina surface to form phosphonates was studied with X‐ray photoelectron spectroscopy (XPS) and polarization modulation infrared reflection‐absorption spectroscopy (PM‐IRRAS). Barrier effects of the resulting layers was assessed by electrochemical polarization curves. With the conditions used in the present work for the self‐assembly reaction, it appears that the sulfur‐containing molecules do not perform as well as CH₃? (CH₂)₁₅? PO(OH)₂ in terms of film quality. Questions are raised about the possibility that the sulfur‐containing molecules could undergo cleavage during surface modification. Copyright © 2008 John Wiley & Sons, Ltd.