Adsorption characteristics of OH-terminated alkanethiol and arenethiol on Au(111) surfaces

Adsorption behaviors of hydroxyl-terminated alkanethiol, 3-mercapto-1-propanol (MPO), and arenethiol, 4-mercaptophenol (MPH), on Au(111) electrodes were studied by cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM). The effects of the molecular structure and the chain length on the characteristics of the self-assembled monolayers (SAMs) were investigated by comparison with the results of 11-mercapto-1-undecanol (MUO) and 6-mercapto-1-hexanol (MHO) reported in the literature. All the alkanethiol SAMs have the same coverage ratio (0.33 ML). For MUO which has a longer chain length, a hexagonal lattice, the (√3 ×√3) structure was observed. However, for shorter thiols (MHO and MPO), the adsorbed molecules exhibit different contrasts under the imaging of STM, ascribed to the different conformations of adsorbed molecules. The CV results indicated that a longer chain length triggers a SAM with higher adhesion and higher resistance to the charge transfer across a SAM. For the SAM of arenethiol, MPH, the π-π stacking interaction of the phenyl ring leads to a lower surface mobility of thiol/Au complexes, lower coverage ratio, and less uniform structure of the adlayer. Furthermore, the vacancy islands commonly observed on alkanethiol-modified Au(111) electrodes do not appear on the MPH-modified surface. Instead, 2-dimensional patch islands formed on the terrace due to the aggregation of moveable MPH/Au complexes.     

Adsorption and Decomposition of Glycerol on Pristine and Oxygen Modified Au(111) Surfaces

Topics in Catalysis - Research on biomass derived raw materials for conventional catalytic processes, especially those directed to replace human dependence on fossil-based energy, is a high...     

硫醇分子在Au(111)表面吸附结构的DFT研究

采用分子模拟方法对硫醇分子在Au(111)表面上的吸附行为进行了研究。对于化学吸附过程,采用了密度泛函理论(DFT)的算法对甲基硫醇和2-巯基乙醇的吸附结构和能量进行了分析。优化结果显示在头基硫原子的多种吸附位置中bridge-fcc位是最稳定的,S-C键相对于金表面法线形成53~54°的倾斜角。对于全覆盖率下的自组装有序结构,采用了分子动力学方法比较了3种不同排布形式的稳定性,结果证明含有3种链取向的C(4×2)结构最稳定。另外,采用DFT方法对电子结构的分析显示,在bridge-fcc吸附位上,硫原子的p电子和邻近的金原子的d电子通过杂化形成了新的成键轨道和反键轨道,这一过程通过对硫和金原子反应前后的局部态密度的分析,进行了详细的论证。     

Creation of Low-Coordination Gold Sites on Au(111) Surface by 1,4-phenylene Diisocyanide Adsorption

The adsorption of CO on a saturated overlayer of 1,4-phenylene diisocyanide (PDI) adsorbed on a Au(111) surface at 300 K is studied using scanning tunneling microscopy (STM), density functional theory (DFT) calculations and reflection absorption infrared spectroscopy (RAIRS). The PDI forms closed-packed rows of gold-PDI chains by extracting gold atoms from the Au(111) substrate. They are imaged by STM and the structure calculated by DFT. The adsorption of CO is studied on the low-coordination gold sites formed on the PDI-covered surface where it adsorbs exhibiting a CO stretching frequency of 2004 cm^?1, consistent with adsorption on an atop site. It is found that CO is stable on heating the sample to ~150 K and is only removed from the surface by heating to ~180 K. Since low-coordination gold atoms are suggested to be the active catalytic sites on supported gold nanoclusters, ??embossing?? the surface to form similar low-coordination sites using PDI might offer a strategy for tailoring the catalytic activity of gold.     

Initial stages of Pt deposition on Au(111) and Au(100)

The deposition of Pt onto unreconstructed Au(111) and Au(100) was studied with cyclic voltammetry and in-situ STM. The latter revealed that in [PtCl₄]²⁻ containing electrolytes, both surfaces are covered by an ordered adlayer of the complex. For the adsorbed [PtCl₄]²⁻ a slightly compressed (√7×√7) R19.1°-structure was assumed for Au(111) and a (3×√10) for Au(100). In both cases, a rather high overpotential for Pt deposition was observed, most probably due to the high stability of the [PtCl₄]²⁻ complex. Nucleation of Pt starts mainly at defects like step edges for low deposition rates and three-dimensional clusters are formed. Due to the high overpotential, some nuclei appear also on terraces at random sites. Higher coverages of Pt lead to a cauliflower like appearance. It is not possible to dissolve the platinum clusters at positive potentials without severely roughening the gold surface. The [PtCl₄]²⁻ complex is oxidized to the [PtCl₆]²⁻ complex at about 0.7 V, when metallic Pt is on the surface.     

Self-assembly of thiolated cyanine aggregates on Au(111) and Au nanoparticle surfaces

Heptamethinecyanine J-aggregates display sharp, intense fluorescence emission making them attractive candidates for developing a variety of chem-bio-sensing applications. They have been immobilized on planar thiol-covered Au surfaces and thiol-capped Au nanoparticles by weak molecular interactions. In this work the self-assembly of novel thiolated cyanine (CNN) on Au(111) and citrate-capped AuNPs from solutions containing monomers and J-aggregates has been studied by using STM, XPS, PM-IRRAS, electrochemical techniques and Raman spectroscopy. Data show that CNN species adsorb on the Au surfaces by forming thiolate-Au bonds. We found that the J-aggregates are preferentially adsorbed on the Au(111) surface directly from the solution while adsorbed CNN monomers cannot organize into aggregates on the substrate surface. These results indicate that the CNN-Au interaction is not able to disorganize the large J-aggregates stabilized by π-π stacking to optimize the S-Au binding site but it is strong enough to hinder the π-π stacking when CNNs are chemisorbed as monomers. The optical properties of the J-aggregates remain active after adsorption. The possibility of covalently bonding CNN J-aggregates to Au planar surfaces and Au nanoparticles controlling the J-aggregate/Au distance opens a new path regarding their improved stability and the wide range of biological applications of both CNN and AuNP biocompatible systems.     

In situ FTIR study of 2-chloropyridine adsorbed on Au(111) and Au(110) electrodes

2-chloropyridine (2Clpy) adsorbed on Au(111) and Au(110) electrodes in 0.1 M KClO₄ containing 2 mM 2Clpy has been investigated using in-situ infrared spectroscopy and differential capacity measurements. For both the electrodes, an in-plane ring vibration due to N-bonded 2Clpy was observed, which was accompanied by a loss in the in-plane ring vibrations due to dissolved 2Clpy. However, the integrated band intensity ratios between the adsorbed 2Clpy and the loss of dissolved 2Clpy for both electrodes are quite different in all potentials measured. The relative band intensity of the N-bonded 2Clpy for Au(110) is much stronger than that for the Au(111). This indicates that for the Au(111) the adsorbed 2Clpy is mainly flat type or the tilt angle of the N-bonded 2Clpy is large. It can be explained by the configuration of adsorbed 2Clpy on the electrode surface. For Au(111) terrace, N-bonded configuration is obstructed by the presence of Cl atom. There is no obstruction for the Au(110) step if the N-bonded 2Clpy is adsorbed on the overtop layer.     

Effect of Au thickness on the evolution of self-assembled Au droplets on GaAs (111)A and (100)

In this paper, we report the effect of Au thickness on the self-assembled Au droplets on GaAs (111)A and (100). The evolution of Au droplets on GaAs (111)A and (100) with the increased Au thickness progress in the Volmer-Weber growth mode results in distinctive 3-D islands. Under an identical growth condition, depending on the thickness of Au deposition, the self-assembled Au droplets show different size and density distributions, while the average height is increased by approximately 420% and the diameter is increased by approximately 830%, indicating a preferential lateral expansion. Au droplets show an opposite evolution trend: the increased size along with the decreased density as a function of the Au thickness. Also, the density shifts on the orders of over two magnitude between 4.23 × 10¹⁰ and 1.16 × 10⁸ cm⁻² over the thickness range tested. At relatively thinner thicknesses below 4 nm, the self-assembled Au droplets sensitively respond to the thickness variation, evidenced by the sharper slopes of dimensions and density plots. The results are systematically analyzed and discussed in terms of atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), cross-sectional surface line profiles, and Fourier filter transform (FFT) power spectra.     

Characterization of Ultra-Thin Films of Pd Deposited on Au(111)

Ultra-thin films (1 and 3 monolayers) of Pd were deposited on the Au(111) surface and then characterized by X-ray photoelectron spectroscopy (XPS), X-ray excited Auger spectroscopy (XAES), low-energy electron diffraction (LEED), and X-ray photoelectron diffraction (XPD). For the 1 ML Pd film annealed at 450 °C, XPS and XAES results indicated that Pd had diffused into the Au substrate. For the 3 ML Pd film deposited at room temperature, the comparison between experimental and theoretical XPD results indicated approximately 30% of the surface was formed by 2 ML Au layers, and 70% of the surface, by 1 ML Au layers.     

Annealing temperature effect on self-assembled Au droplets on Si (111)

We investigate the effect of annealing temperature on self-assembled Au droplets on Si (111). The annealing temperature is systematically varied while fixing other growth parameters such as deposition amount and annealing duration clearly to observe the annealing temperature effect. Self-assembled Au droplets are fabricated by annealing from 50°C to 850°C with 2-nm Au deposition for 30 s. With increased annealing temperatures, Au droplets show gradually increased height and diameter while the density of droplets progressively decreases. Self-assembled Au droplets with fine uniformity can be fabricated between 550°C and 800°C. While Au droplets become much larger with increased deposition amount, the extended annealing duration only mildly affects droplet size and density. The results are systematically analyzed with cross-sectional line profiles, Fourier filter transform power spectra, height histogram, surface area ratio, and size and density plots. This study can provide an aid point for the fabrication of nanowires on Si (111).     

The adsorption of methyl nitrite on the Au(111) surface

The interaction of the methyl nitrite molecule (CH₃ONO) with the gold(111) surface has been studied by means of density functional calculations. The perfect Au(111) surface has been represented by a rather large cluster model, Au₂₂, that was in turn used to extract information about the preferred adsorption geometry of the CH₃ONO species. Vibrational frequencies and adsorption energy are also reported. The calculated adsorption energies are 31.2 kJ/mol with respect to gas phase cis-conformer and 35.1 kJ/mol with respect to trans-methyl nitrite, very close to the experimental adsorption energy of 33.5 kJ/mol. From the analysis of vibrational frequencies of gas phase and adsorbed species it is concluded that only the cis-conformer is present at the Au(111) surface.     

From the nucleation of wiggling Au nanostructures to the dome-shaped Au droplets on GaAs (111)A, (110), (100), and (111)B

In this paper, the systematic evolution process of self-assembled Au droplets is successfully demonstrated on GaAs (111)A, (110), (100), and (111)B. On various GaAs substrates, self-assembled Au clusters begin to nucleate at around 300°C, and then, they develop into wiggly Au nanostructures at 350°C. Between 400°C and 550°C, the self-assembled dome-shaped Au droplets with fine uniformity are fabricated with various sizes and densities based on the Volmer-Weber growth mode. Depending on the annealing temperature, the size including the average height and lateral diameter and the density of Au droplets show the opposite trend of increased size with correspondingly decreased density as a function of the annealing temperature due to the difference in the diffusion length of adatoms at varied activation energy. Under an identical growth condition, depending on the surface index, the size and density of Au droplets show a clear distinction, observed throughout the temperature range. The results are systematically analyzed and discussed in terms of atomic force microscopy (AFM) images, cross-sectional line profiles, and Fourier filter transform (FFT) power spectra as well as the summary plots of the size and density.     

Pd deposition onto Au(111) from nitrate solution

The initial stages of palladium deposition onto Au(111) from 0.1 M HNO₃ + 0.2 mM Pd(NO₃)₂ have been studied by cyclic voltammetry and in situ scanning tunnelling microscopy. It is demonstrated that nucleation starts exclusively at surface defects such as monoatomic high steps, which is at variance with recently published work. From this and our previous work it thus appears that surface defects are the preferred nucleation sites indeed for nitrate, sulphate and chloride containing solutions.     

Pd(111) versus Pd–Au(111) in carbon monoxide oxidation under elevated pressures

The oxidation of CO on Pd(111) and Pd₇₀Au₃₀(111) has been studied under pressures upto 100 Torr. Gold is found to decrease the surface activity by inhibiting oxygen dissociation. For a sufficient conversion time depending on the CO coverage and the surface identity, a dramatic boost of activity occurs. This is ascribed to a switch from CO-induced inhibition of O₂ adsorption to a regime determined by CO adsorption. The other kinetic features are explained by oxidation of palladium and adsorption-induced restructuring of the surfaces.     

Pt/Au(111)表面合金电化学稳定性的第一性原理研究

利用密度泛函理论(DFT)对Pt/Au (111)表面合金的电化学稳定性进行了初步研究。形成能计算结果表明,Au与Pt不易在块体中形成合金,但能在Pt (111)面形成表面合金。溶解电位计算结果进一步表明,Pt/Au (111)面上Pt原子的溶解电位与其第一近邻Au原子数有很好的线性关系,而Au对第二近邻及更远近邻的Pt溶解电位的影响可忽略。这些结果意味着可建立表面配位环境与表面原子溶解电位间的标度关系,为揭示表面合金的结构-电化学稳定性构型关系奠定了基础。     

Molecular adsorption on V2O3(0001)/Au(111) surfaces

The adsorption of carbon monoxide (CO), propane (C₃H₈) and propene (C₃H₆) on V₂O₃(0001) films grown on Au(111) was studied by Temperature Programmed Desorption (TPD) and X-ray Photoelectron Spectroscopy (XPS). The “oxidized” surface (i.e., as prepared exhibiting V=O termination), the “reduced” surface (i.e., V=O groups being removed by electron irradiation), as well as the oxygen pre-covered reduced surface were investigated. Both TPD and XPS indicate that the oxidized surface has little affinity for CO adsorption, while the reduced surface readily binds CO (CO amount approx. 10 times higher). Accordingly, CO can be used to titrate the presence or absence of vanadyl oxygen (via adsorption on the vanadium atoms) but also of defects like surface oxygen vacancies. For propane and propene, desorption of the parent molecules was the major process, i.e., surface reactions were absent under the applied conditions. When oxygen was pre-adsorbed on the reduced surface, the adsorption properties resembled that of the oxidized surface, i.e., the vanadyl groups were (partially) re-established. TPD and XPS provide a handle to differentiate the binding sites on the V₂O₃ surface. Dedicated to Prof. Konrad Hayek.     

Influence of halide anions on the behavior of pyridine adsorbed on Au(111) electrode

The effect of halide anions on pyridine-d₅ adsorbed on Au(111) electrode has been studied in neutral solutions containing F⁻, Cl⁻, and Br⁻ by IRAS and differential capacity measurement. In the NaF solution, N-bonded pyridine increases up to 0.1 V, and a new adsorbed state due to the N-bonded type grows at positive potentials. In the NaCl solution, the N-bonded type grows at all of adsorbed potential except for the appearance of the new adsorbed state at 0.2 V. In the NaBr containing solution, the new adsorbed state is not observed. In the NaCl and NaBr solutions, the total amount of the N-bonded pyridine is suppressed at positive potentials. We propose that the new band is attributed to an ordered layer of the N-bonded pyridine on the Au(111) electrode, and that the formation of the ordered layer is inhibited by the adsorption of Cl⁻ and Br⁻.