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.     

pH Dependent Molecular Self-Assembly of Octaphosphonate Porphyrin of Nanoscale Dimensions: Nanosphere and Nanorod Aggregates

Self-assembled nanostructures of zwitterionic octaphosphanatoporphyrin 1, of either nanoparticles or nanorods, depending on small changes in the pH, is demonstrated based on the J-aggregates. Porphyrin 1 self-assembled into nanosphere aggregates with a diameter of about 70-80 nm in the pH range 5-7, and nanorod aggregates were observed at pH 8.5. Hydrogen bonding, π-π stacking and hydrophilic interactions play important roles in the formation of this nanostructure morphology. Nanostructures were characterized by UV/Vis absorbance, fluorescence, atomic force microscopy (AFM) and transmission electron microscopy (TEM). This interesting pH dependent self-assembly phenomenon could provide a basis for development of novel biomaterials.     

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.     

The bonding in thiolate protected gold nanoparticles from Au4f photoemission core level shifts

Density functional theory calculations are used to evaluate Au4f core level shifts of methyl thiolate protected Au(25), Au(102) and Au(144) nanoparticles. The shifts are found to provide sensitive fingerprints of the chemical environment. In particular, Au atoms in protective gold-thiolate complexes have higher binding energies than Au atoms with solely metal neighbors. The core level shifts for the nanoparticles are compared to the corresponding results for methyl thiolates adsorbed on Au(111) and implications for the understanding of the gold-sulfur bond is discussed.     

Nanocomposites of size-controlled gold nanoparticles and graphene oxide: formation and applications in SERS and catalysis

In this paper, we describe the formation of Au nanoparticle-graphene oxide (Au-GO) and -reduced GO (Au-rGO) composites by noncovalent attachment of Au nanoparticles premodified with 2-mercaptopyridine to GO and rGO sheets, respectively, viaπ-π stacking and other molecular interactions. Compared with in situ reduction of HAuCl4 on the surface of graphene sheets that are widely used to prepare Au-GO composites, the approach developed by us offers well controlled size, size distribution, and morphology of the metal nanoparticles in the metal-GO nanohybrids. Moreover, we investigated surface enhanced Raman scattering (SERS) and catalysis properties of the Au-graphene composites. We have demonstrated that the Au-GO composites are superior SERS substrates to the Au NPs. Similarly, a comparative study on the catalytic activities of the Au, Au-GO, and Au-rGO composites in the reduction of o-nitroaniline to 1,2-benzenediamine by NaBH4 indicates that both Au-GO and Au-rGO composites exhibit significantly higher catalytic activities than the corresponding Au nanoparticles.     

A general and efficient method for decorating graphene sheets with metal nanoparticles based on the non-covalently functionalized graphene sheets with hyperbranched polymers

Multipyrene terminated hyperbranched polyglycidol (mPHP) has been synthesized and used to non-covalently functionalize pristine graphene sheets (GSs) through π-π stacking interactions. Mediated by the mPHP layer, a variety of metal nanoparticles (Au, Ag and Pt) were in situ generated and deposited onto the surface-modified GS, yielding versatile GS/mPHP/metal nanohybrids. As typical examples, by simply controlling the concentration of HAuCl(4) used, Au nanostructures ranging from isolated spheres to a continuous film were created and coated onto the surface-modified GS. The studies on the fluorescence properties of resulting GS/mPHP/Au hybrid nanostructures reveal that the GS and controllable content of Au components in the hybrids can effectively quench the fluorescence emission of mPHP in a controlled manner. Further investigation indicates that GS/mPHP/Au hybrids are promising surface enhanced Raman scattering (SERS) substrates. The SERS activities of these hybrids depend on the contents and form of the Au. The GS/mPHP/Au hybrid containing continuous Au films exhibits the strongest SERS activity. GS/mPHP/Au hybrids are also used as efficient heterogeneous catalysts for the reduction of 4-NP, and demonstrate excellent catalytic performance. The detailed reaction kinetics and the reusability of such catalysts have also been investigated.     

In/Au(111)和Ir/Au(111)面上巴豆醛选择加氢的机理研究及比较

基于巴豆醛在M/Au（111）合金表面（M=In,Ir）垂直吸附的最稳定吸附结构,采用密度泛函理论对其不完全加氢的反应机理进行探究。从不同加氢机理下各基元反应的活化能、反应热计算以及构型变化分析中可知,巴豆醛在M/Au（111）面上均优先对距离合金表面较近的C＝O进行加氢,且以C为活性中心优先进行加氢为最优机理,其中第1步加氢反应的活化能较高,是该机理的控速步骤。反应物巴豆醛的O原子与合金的掺杂原子M形成较强的化学吸附,提高了M/Au（111）面对C＝O加氢的选择性。巴豆醛按最优机理加氢的基元反应中在In/Au（111）面上最高反应能垒为0.969 eV,比在Ir/Au（111）面的最高反应能垒1.332 eV低,因此认为In/Au合金对其不完全加氢有更好的催化活性。     

STM-induced light emission from thin films of perylene derivatives on the HOPG and Au substrates

We have investigated the emission properties of N,N'-diheptyl-3,4,9,10-perylenetetracarboxylic diimide thin films by the tunneling-electron-induced light emission technique. A fluorescence peak with vibronic progressions with large Stokes shifts was observed on both highly ordered pyrolytic graphite (HOPG) and Au substrates, indicating that the emission was derived from the isolated-molecule-like film condition with sufficient π-π interaction of the perylene rings of perylenetetracarboxylic diimide molecules. The upconversion emission mechanism of the tunneling-electron-induced emission was discussed in terms of inelastic tunneling including multiexcitation processes. The wavelength-selective enhanced emission due to a localized tip-induced surface plasmon on the Au substrate was also obtained.     

Impediment to heterogeneous electron transfer reactions of redox-active species by alkanedithiol self-assembled monolayers with and without an adlayer of Au nanoparticles

The impediment of heterogeneous electron transfer (ET) reactions of several electroactive species by alkanedithiol self-assembled monolayers (SAMs) and those covered with Au nanoparticles was investigated. It was found that, when densely packed 1,6-hexanedithiol and 1,9-nonanedithiol SAMs were formed with and without adsorbed gold nanoparticles, Fe(CN)₆³⁻ reduction became extremely sluggish. The attachment of Au nanoparticles does not appear to improve the electronic communication between the solution species and the underlying Au electrode surface. On the other hand, Ru(NH₃)₆³⁺ and ferrocenecarboxylic acid both exhibited quasi-reversible redox waves at these surfaces. The variation of impediment were attributed to the different electron transfer mechanisms for these redox species. The adsorption of Au nanoparticles onto alkanedithiol SAMs was estimated by flow injection quartz crystal microbalance (FI-QCM), showing a rapid adsorption process. Amounts of Au nanoparticles did not vary between the two different alkanedithiols. Finally, we quantified the adsorption of Au nanoparticles at the QCM crystal modified with a 1,9-nonanedithiol SAM in air. A surface coverage of 2.56% was obtained.     

The effects of the π-π stacking interactions on the patterns of gold nanoparticles formed at the air-water interface

Benzyl-n-hexadecyl dimethylammonium chloride (BHDC) monolayer-stabilized gold nanoparticles were synthesized in a two-phase liquid-liquid system and found to self-assemble into varied structures under the control of temperature at the air-water interface. It has been demonstrated that the π-π stacking interactions between the capping agent molecules significantly affect the formation of the unique patterns. A possible mechanism based on Marangoni-Bénard convection in the evaporating droplets and π-π stacking interactions was proposed. Four surfactants with similar structures: N-hexadecyl-N-methylpyrrolidinium bromide (C(16)MPB), 1-hexadecyl-3-methylimidazolium bromide (C(16)mimBr), 1-(2,4,6-trimethylphenyl)-3-hexadecylimidazolium bromide (C(16)pimBr) and hexadecyltrimethylammonium bromide (CTAB) were also used to further verify the formation mechanism mentioned above.     

Functionalization of reduced graphene oxide nanosheets via stacking interactions with the fluorescent and water-soluble perylene bisimide-containing polymers

Reduced graphene oxide (RGO)-polymer composites were prepared via π-π stacking interactions of RGO with the perylene bisimide-containing poly(glyceryl acrylate) (PBIPGA). PBIPGA was synthesized via atom transfer radical polymerization (ATRP) of solketal acrylate (SA), using bifunctional N,N′-bis{2-[2-[(2-bromo-2-methylpropanoyl)oxy]ethoxy]ethyl}perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI-Br) as the initiator, and subsequent hydrolysis of the acetal-protecting group. PBIPGA was characterized by ¹H NMR spectroscopy, gel permeation chromatography (GPC), UV-visible absorption spectroscopy and fluorescence spectroscopy. The presence of π-π stacking interactions between PBI and the RGO surface was suggested by fluorescence and UV-visible absorption spectroscopy results. The chemical states and π-π stacking interaction, morphology, and composition of RGO-PBIPGA composites were characterized, respectively, by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The low cytotoxicity level of the RGO-PBIPGA composites was revealed by incubation with 3T3 fibroblasts in 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assays in vitro.     

Hydrogen evolution during the oxidation of formaldehyde on Au:: The influence of single crystal structure and Tl-upd

Hydrogen evolution during formaldehyde oxidation in alkaline solution has been monitored by Differential Electrochemical Mass Spectrometry on Au(111) and polycrystalline gold. The current efficiency for hydrogen evolution increases with higher concentration and is in the same range on both, polycrystalline Au and Au(111) electrode. The onset potentials and half-wave potentials are higher on Au(111). Reaction orders for the faradaic current on the bare gold electrodes have been determined as 0.21 for higher and 0.76 for lower concentrations. Reaction orders for hydrogen evolution during formaldehyde oxidation are 1.4 times higher in each case. Tafel slopes in the range of 140–160 mV are found. This signifies that the first reaction step involving the formation of adsorbed hydrogen is largely determining the overall reaction rate. In the presence of thallium adlayers hydrogen evolution from formaldehyde oxidation is largely suppressed. On the thallium modified polycrystalline Au, formaldehyde oxidation is shifted for 100 mV to higher potentials where Tl is partially desorbed and hydroxide is coadsorbed on the modified surface. On thallium modified Au(111), a similar process takes place, but in the same potential region as the onset of formaldehyde oxidation on the bare surface and therefore the formaldehyde oxidation is only slightly shifted. Tafel slopes are decreased to 80 mV/dec in the presence of thallium. In the presence of adsorbed thallium, the first reaction step is in equilibrium, the coverage with adsorbed hydrogen is smaller and its recombination to H₂ is largely suppressed.     

Hydrogen evolution during the oxidation of formaldehyde on Au:: The influence of single crystal structure and Tl-upd

Hydrogen evolution during formaldehyde oxidation in alkaline solution has been monitored by Differential Electrochemical Mass Spectrometry on Au(111) and polycrystalline gold. The current efficiency for hydrogen evolution increases with higher concentration and is in the same range on both, polycrystalline Au and Au(111) electrode. The onset potentials and half-wave potentials are higher on Au(111). Reaction orders for the faradaic current on the bare gold electrodes have been determined as 0.21 for higher and 0.76 for lower concentrations. Reaction orders for hydrogen evolution during formaldehyde oxidation are 1.4 times higher in each case. Tafel slopes in the range of 140-160 mV are found. This signifies that the first reaction step involving the formation of adsorbed hydrogen is largely determining the overall reaction rate. In the presence of thallium adlayers hydrogen evolution from formaldehyde oxidation is largely suppressed. On the thallium modified polycrystalline Au, formaldehyde oxidation is shifted for 100 mV to higher potentials where Tl is partially desorbed and hydroxide is coadsorbed on the modified surface. On thallium modified Au(111), a similar process takes place, but in the same potential region as the onset of formaldehyde oxidation on the bare surface and therefore the formaldehyde oxidation is only slightly shifted. Tafel slopes are decreased to 80 mV/dec in the presence of thallium. In the presence of adsorbed thallium, the first reaction step is in equilibrium, the coverage with adsorbed hydrogen is smaller and its recombination to H₂ is largely suppressed.     

Multifunctional Nanoaggregates Composed of Active CPUL1 and a Triphenylphosphine Derivative for Mitochondria-Targeted Drug Delivery and Cell Imaging

We report that active substance (CPUL1) and triphenylphosphine (TPP) derivative could self-assemble into multifunctional nanoaggregates (CPUL1−TPP NAs) through electrostatic and π-π stacking interactions. CPUL1 was wrapped tightly inside the nanoparticles as well as CPUL1 and TPP derivative self-assembled into stable and compact nanoparticles in water. The positive surface charge of CPUL1−TPP NAs made them much easier to be endocytosed to enter cytoplasm, accumulate in the mitochondria and induce cell apoptosis based on their mitochondria targeting ability, fluorescence property and fast cell uptake characteristic, which showed better antitumor efficacy on HUH7 hepatoma cells in vitro than that of free CPUL1.     

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.     

Graphene growth on Pt(111) and Au(111) using a MBE carbon solid-source

In this work we present a Molecular Beam Epitaxy (MBE) growth method to obtain graphene on noble metals using evaporation of carbon atoms from a carbon solid-source in ultra-high vacuum conditions. We have synthesized graphene (G) on different metal surfaces: from a well studied substrate as platinum, to a substrate where it can only be formed using innovative methods, as is the case of gold. For the characterization of the graphene layers we have used in situ surface science techniques as low energy electron diffraction (LEED), auger electron spectroscopy (AES) and scanning tunneling microscopy (STM).One of the main advantages of our methodology is that low surface temperatures are required to form graphene. Thus, by annealing Pt(111) and Au(111) substrates up to 650 °C and 550 °C respectively during carbon evaporation, we have obtained the characteristic LEED diagrams commonly attributed to graphene on these surfaces. STM results further prove the formation of graphene. For the case of G on Pt(111), STM images show a long range ordering associated with moiré patterns that correspond to a monolayer of graphene on (111) platinum surface. On the other hand, G/Au(111) STM results reveal the formation of dendritic islands pinned to atomic step edges. This method opens up new possibilities for the formation of graphene on many different substrates with potential technological applications.     

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.     

Investigation of CO Oxidation Transient Kinetics on an Oxygen Pre-covered Au(211) Stepped Surface

The desire to explain the origin(s) of the unexpected catalytic activity of oxide-supported Au nanoparticles for CO oxidation discovered by Haruta and coworkers has stimulated numerous experimental and theoretical studies of Au nanoclusters in the gas phase and on metal oxide supports, and on Au single-crystal surfaces. In order to explore further the reactivity of low-coordination Au step sites, we have performed transient kinetics studies of CO oxidation on an O-precovered, stepped Au(211) single crystal surface. We found behavior similar to that observed previously on flat Au(111) and (110) surfaces; i.e., there is no evidence in these transient kinetics for any special reactivity associated with this stepped Au surface. The CO oxidation reaction rate was highly dependent on the initial oxygen coverage, and we determined an apparent activation energy for CO oxidation of ?7.0 kJ mol^?1 for θ _O ^init  = 0.9 ML. Within the Langmuir-Hinschelwood (LH) reaction scheme, we estimate an activation energy of E _LH = 20–43 kJ mol^?1 on this surface for CO oxidation via this pathway. This is somewhat below the value of 67 kJ mol^?1 predicted by recent theoretical calculations.     

Electrical and Optical Properties of Conducting Poly(3-hexylthiophene)/Multi-walled Carbon Nanotube System

Polymer multi-wall carbon nanotube (MWNT) composites were prepared and characterized as part of an effort to develop polymeric materials with improved combinations of properties for potential use in solar cell applications. Multi-walled carbon nanotube (MWNT) poly(3-hexylthiophene) nanocomposites were synthesized by in situ polymerization of monomers in the presence of different amounts of MWNTs. A process is reported to efficiently disperse multi-walled carbon nanotube (MWNT) bundles in a semiconducting polymer matrix. A uniform dispersion of the nanotubes in the polymer matrix was obtained. Characterization of the nanocomposites and the effects of MWNT concentration and dispersion on the structural, optical and electrical properties were discussed. FTIR and Raman spectroscopic investigations of nanocomposites indicate that the polymer is wrapped on the nanotubes, taking up a rigid orientation through π-π stacking. The Hall voltage measurement is followed to monitor carrier concentrations and mobilities, instead of the device fabrication and hole mobility measurements.     

Scanning probe microscopy study of chemical vapor deposition grown graphene transferred to Au(111)

Graphene is grown by chemical vapor deposition (CVD) on copper films and transferred ex situ to atomically flat Au(111) films, after which the sample is annealed in ultra-high vacuum (UHV) prior to scanning tunneling microscopy (STM) investigation. STM imaging at 78 K reveals large, clean and defect-free atomically flat areas that are separated by graphene wrinkles and grain boundaries. In addition to the graphene atomic structure, the flat surface regions exhibit patterns with larger periodicity that can be interpreted as Moiré patterns formed by the atomic lattices of the graphene and the gold. Our findings show that the CVD growth and ex situ transfer of graphene (G) to atomically flat Au(111) surfaces allows obtaining clean and high-quality G/Au surfaces that are suitable for in situ deposition of, e.g., molecules and atoms, for UHV investigation purposes. This approach may offer a higher degree of freedom in preparing bare and doped graphene on atomically flat surfaces compared to a full in situ approach.