Alloy formation during the electrochemical growth of a Ag-Cd ultrathin film on Au(1 1 1)

The electrodeposition of a Ag/Cd ultrathin film on a Au(1 1 1) surface and the formation of a surface alloy during this process have been studied using classical electrochemical techniques and in situ Scanning Tunneling Microscopy (STM). The films were obtained from separate electrolytes containing Ag⁺ or Cd²⁺ ions and from a multicomponent solution containing both ions. First, the polarization conditions were adjusted in order to form a Ag film by overpotential deposition. Afterwards, a Cd monolayer was formed onto this Au(1 1 1)/Ag modified surface by underpotential deposition. The voltammetric behavior of the Cd UPD and the in situ STM images indicated that the ultrathin Ag films were uniformly deposited and epitaxially oriented with respect to the Au(1 1 1) surface. Long time polarization experiments showed that a significant Ag-Cd surface alloying accompanied the formation of the Cd monolayer on the Au(1 1 1)/Ag modified surface, independent of the Ag film thickness. In the case of an extremely thin Ag layer (1 Ag ML) the STM images and long time polarization experiments revealed a solid state diffusion process of Cd, Ag, and Au atoms which can be responsible for the formation of different Ag-Cd or Au-Ag-Cd alloy phases.     

Preparation and characterization of TiO2 photocatalysts by Fe doping together with Au deposition for the degradation of organic pollutants

Fe³⁺ doped TiO₂ deposited with Au (Au/Fe–TiO₂) was successfully prepared with an attempt to extend light absorption of TiO₂ into the visible region and reduce the rapid recombination of electrons and holes. The samples were characterized by X-ray diffraction (XRD), N₂ physical adsorption, Raman spectroscopy, atomic absorption flame emission spectroscopy (AAS), UV–vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectra. The photocatalytic activities of the samples were evaluated for the degradation of 2,4-chlorophenol in aqueous solutions under visible light (λ > 420 nm) and UV light irradiation. The results of XRD, XPS and high-resolution transmission electron microscopy (HRTEM) analysis indicated that Fe³⁺ substituted for Ti⁴⁺ in the lattice of TiO₂, Au existed as Au⁰ on the surface of the photocatalyst and the mean particle size of Au was 8 nm. Diffuse reflectance measurements showed an extension of light absorption into the visible region for Au/Fe–TiO₂, and PL analysis indicated that the electron–hole recombination rate has been effectively inhibited when Au deposited on the surface of Fe-doped TiO₂. Compared with Fe doped TiO₂ sample and Au deposited TiO₂ sample, the Au/Fe–TiO₂ photocatalyst exhibited excellent visible light and UV light activity and the synergistic effects of Fe³⁺ and Au was responsible for improving the photocatalytic activity.     

Cadmium cathodic deposition on polycrystalline p-selenium: Dark and photoelectrochemical processes

Cathodic reduction of Cd²⁺ on p-Se proceeds at low overpotential in the dark and results in bulk Cd, while the underpotential deposition is kinetically inhibited. Cadmium adlayer is photoelectrochemically deposited on illuminated electrode 0.7 V above E(Cd²⁺/Cd). The adlayer cathodic deposition under illumination proceeds with simultaneous formation of CdSe nanoparticles. Potentiodynamic electrochemical impedance spectroscopy has discriminated the two products of the photoelectrochemical reaction both by their potentials of anodic oxidation and by characteristic dependences of impedance on potential. Anodic oxidation of CdSe nanoparticles gives a sharp peak of real impedance in low frequencies close to the corresponding anodic current peak in cyclic voltammogram. The impedance peak appears below a threshold frequency f_t. The latter separates two modes of diffusion in anodic dissolution of CdSe nanoparticles. The diffusion proceeds independently at different particles above f_t and turns to cooperative mode below the threshold frequency. Due to this effect, information on spatial distribution of growing nuclei on electrode surface in early stages of electrodeposition can be obtained from potentiodynamic impedance spectra.     

Studying the localized deposition of Ag nanoparticles on self-assembled monolayers by scanning electrochemical microscopy (SECM)

The local deposition of Ag nanoparticles (NPs) on ω-mercaptoalkanoic acid, HS(CH₂)_nCO₂H, (n = 2, 10) self-assembled monolayers (SAMs) by scanning electrochemical microscopy (SECM) is reported. We found that the presence of a SAM had a pronounced effect on Ag deposition. Experiments were conducted by applying different potentials to an Au(1 1 1) substrate either in the presence of a constant concentration of Ag⁺ ions in solution (bulk deposition) or by generating a flux of Ag⁺ from an Ag microelectrode that was positioned close to the Au(1 1 1) substrate (SECM deposition). SECM was used for generating a controlled flux of silver ions by anodic dissolution of an Ag microelectrode close to the SAMs modified Au(1 1 1). We found that the shape of the NPs was affected by the length of the carbon-chain of the SAM. Tetrahedral NPs were obtained on bare Au(1 1 1) surfaces while rod like and cubic Ag NPs were deposited onto 3-mercaptopropanoic acid (MPA) and 11-mercaptoundecanoic acid (MUA) SAMs, respectively. The size and shape of the deposited NPs were influenced by the deposition potential.We conclude that the shape and distribution of locally deposited Ag NPs on Au(1 1 1) can be controlled by modification of the substrate with a SAM and through controlling the Ag⁺ flux generated by SECM.     

A Comparative Study on the Biosorption of Cd2+ onto Paecilomyces lilacinus XLA and Mucoromycote sp. XLC

The filamentous fungi XLA and XLC isolated from Cd-contaminated soil were identified morphologically and phylogenetically as Paecilomyces lilacinus and Mucoromycote sp., respectively. The minimum inhibitory concentrations (MICs) of Cd²⁺, Co²⁺, Cu²⁺, Zn²⁺, Cr³⁺ and Cr⁶⁺ in minimum mineral (MM) medium agar plates were 29,786, 2945, 9425, 5080, 1785 and 204 mg·L⁻¹ for XLA and 11,240, 884, 9100, 2540, 3060 and 51 mg·L⁻¹ for XLC, respectively. Favorable biosorption conditions for adsorption of Cd²⁺ by the tested fungi were investigated. Efficient performances of the biosorbents were described using Langmuir isotherm model, and the predicted maximum biosorption capacities for Cd²⁺ were 77.61 mg·g⁻¹ of XLA and 79.67 mg·g⁻¹of XLC. Experiments on desorption potential of biosorbents validated their efficacy at a large scale. Results showed that XLA obtained a desorption rate of 84.7% by 2% EDTA and XLC gained a desorption rate of 78.9% by 0.1 M HCl. Analysis by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) and X-ray photoelectron spectroscopy (XPS) suggested that groups of C–N, COO– for XLA and C–N, CH₂ and phosphate for XLC were the dominant binding sites for Cd²⁺ biosorption. Our results indicated that the fungus XLA, rather than XLC, could potentially be used as an inexpensive, eco-friendly and effective bioremediation agent for the removal of Cd²⁺ from wastewater.     

Underpotential deposition of cadmium adatoms on Te and CdTe

Underpotential deposition (UPD) of Cd adatoms onto the surface of Te and CdTe films in Cd²⁺-containing solutions has been studied using electrochemical methods and AFM. The electrochemical deposition of Cd adatoms on Te and CdTe begins at potentials 400 mV more positive than the reversible potential of Cd²⁺/Cd couple and proceeds irreversibly. A strong chemical interaction of Cd adatoms with the surface Te atoms is the driving force of the UPD process. The deposition of Cd adatoms on the tellurium surface is accompanied by their stepwise interaction with tellurium to give CdTe nanophase.     

Insights into the surface and redox properties of single-walled carbon nanotube—cobalt(II) tetra-aminophthalocyanine self-assembled on gold electrode

This paper describes for the first time the electrochemical properties of redox-active self-assembled films of single-walled carbon nanotubes (SWCNTs) coordinated to cobalt(II)tetra-aminophthalocyanine (CoTAPc) by sequential self-assembly onto a preformed aminoethanethiol (AET) self-assembled monolayer (SAM) on a gold electrode. Both redox-active SAMs (Au-AET-SWCNT and Au-AET-SWCNT-CoTAPc) exhibited reversible electrochemistry in aqueous (phosphate buffer) solution. X-ray photoelectron spectroscopy (XPS) confirmed the appearance on the gold surface of the various elements found on the SAMs. Atomic force microscopy (AFM) images prove, corroborating the estimated electrochemical surface concentrations, that these SAMs lie normal to the gold surface. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)₆]^3−/4− as a redox probe revealed that the Au-AET-SWCNT-CoTAPc showed much lower (∼10 times) electron-transfer resistance (R_et) and much higher (∼10 times) apparent electron-transfer rate constant (k_app) compared to the Au-AET-SWCNT SAM. Interestingly, a preliminary electrocatalytic investigation showed that both SAMs exhibit comparable electrocatalytic responses towards the detection of dopamine in pH 7.4 phosphate buffer solutions (PBS). The electrochemical studies (cyclic voltammetry (CV) and EIS) prove that SWCNT greatly improves the electronic communication between CoTAPc and the Au electrode surface.     

Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode

Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards l-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for l-cysteine at potentials where metal oxidation (M^III/M^II) takes place and this metal oxidation mediates the catalytic oxidation of l-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards l-cysteine at potentials where Mn^IV/Mn^III redox peak occurs and this redox peak mediates l-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10⁻⁷ mol L⁻¹ and good linearity for a studied concentration range up to 60 μmol L⁻¹.     

Effect of deposition voltage on the microstructure of electrochemically deposited hydrogenated amorphous carbon films

Hydrogenated amorphous carbon (a-C:H) films were deposited on Si substrates by electrolysis in a methanol solution at ambient pressure and a low temperature (50 °C), using various deposition voltages. The influence of deposition voltage on the microstructure of the resulting films was analyzed by visible Raman spectroscopy at 514.5 nm and X-ray photoelectron spectroscopy (XPS). The contents of sp³ bonded carbon in the various films were obtained by the curve fitting technique to the C1s peak in the XPS spectra. The hardness and Young’s modulus of the a-C:H films were determined using a nanoindenter. The Raman characteristics suggest an increase of the ratio of sp³/sp² bonded carbon with increasing deposition voltage. The percentage of sp³-bonded carbon is determined as 33–55% obtained from XPS. Corresponding to the increase of sp³/sp², the hardness and Young’s modulus of the films both increase as the deposition voltage increases from 800 V to 1600 V.     

Surface properties of self-assembled monolayer films of tetra-substituted cobalt, iron and manganese alkylthio phthalocyanine complexes

Self-assembled monolayer (SAM) films of iron (SAM-1), cobalt (SAM-2) and manganese (SAM-3) phthalocyanine complexes, tetra-substituted with diethylaminoethanethio at the non-peripheral positions, were formed on gold electrode in dimethylformamide (DMF). Electrochemical, impedimentary and surface properties of the SAM films were investigated. Cyclic voltammetry was used to investigate the electrochemical properties of the films. Ability of the films to inhibit common faradaic processes on bare gold surface (gold oxidation, solution redox chemistry of [Fe(H₂O)₆]³⁺/[Fe(H₂O)₆]²⁺ and underpotential deposition (UDP) of copper) was investigated. Electrochemical impedance spectroscopy (EIS), using [Fe(CN)₆]^3−/4− redox process as a probe, offered insights into the electrical properties of the films/electrode interfaces. Surface properties of the films were probed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The films were employed for the electrocatalytic oxidation of the pesticide, carbofuran. Electrocatalysis was evidenced from enhanced current signal and less positive oxidation potential of the pesticide on each film, relative to that observed on the bare gold electrode. Mechanism of electrocatalytic oxidation of the pesticide was studied using rotating disc electrode voltammetry.     

PcNRAMP1 Enhances Cadmium Uptake and Accumulation in Populus × canescens

Poplars are proposed for the phytoremediation of heavy metal (HM) polluted soil. Characterization of genes involved in HM uptake and accumulation in poplars is crucial for improving the phytoremediation efficiency. Here, Natural Resistance-Associated Macrophage Protein 1 (NRAMP1) encoding a transporter involved in cadmium (Cd) uptake and transport was functionally characterized in Populus × canescens. Eight putative PcNRAMPs were identified in the poplar genome and most of them were primarily expressed in the roots. The expression of PcNRAMP1 was induced in Cd-exposed roots and it encoded a plasma membrane-localized protein. PcNRAMP1 showed transport activity for Cd²⁺ when expressed in yeast. The PcNRAMP1-overexpressed poplars enhanced net Cd²⁺ influxes by 39–52% in the roots and Cd accumulation by 25–29% in aerial parts compared to the wildtype (WT). However, Cd-induced biomass decreases were similar between the transgenics and WT. Further analysis displayed that the two amino acid residues of PcNRAMP1, i.e., M236 and P405, play pivotal roles in regulating its transport activity for Cd²⁺. These results suggest that PcNRAMP1 is a plasma membrane-localized transporter involved in Cd uptake and transporting Cd from the roots to aerial tissues, and that the conserved residues in PcNRAMP1 are essential for its Cd transport activity in poplars.     

Enhanced photoelectrocatalytic activity of FTO/WO3/BiVO4 electrode modified with gold nanoparticles for water oxidation under visible light irradiation

Gold nanoparticles were successfully deposited on FTO/WO₃/BiVO₄ electrode surface by means of electrolysis of AuCl₄⁻ ions. The composite films were characterized by SEM, XPS and XRD techniques. An increase in photocurrent and a negative shift of onset potential for water oxidation were observed upon modification of the electrode surface with the Au particles. The electrochemical impedance spectroscopy was used to confirm the acceleration of charge transfer process by Au deposition at the electrode surface. The photocurrent action spectrum did not correlate with the plasmonic absorbance of Au nanoparticles at 560 nm, suggesting that the Au nanoparticles increased charge separation without undergoing a plasmon resonance effect under visible light irradiation.     

Biological synthesis of bimetallic Au/Ag nanoparticles using Persimmon (<Emphasis Type="Italic">Diopyros kaki</Emphasis>) leaf extract

Persimmon (Diopyros kaki) leaf extract was used for the synthesis of bimetallic Au/Ag nanoparticles. Competitive reduction of Au³⁺ and Ag⁺ ions present simultaneously in solution during exposure to Persimmon leaf extract leads to the formation of bimetallic Au/Ag nanoparticles. UV-visible spectroscopy was monitored as a function of reaction time to follow the formation of Au/Ag nanoparticles. The synthesized bimetallic Au/Ag nanoparticles were characterized with energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). SEM images showed that large Au/Ag particles of 50–500 nm were formed with some cubic structure, while pure Ag particles obtained by reduction of only Ag+ ion were smaller with diameter of 15–90 nm and predominantly spherical. The atomic Ag contents of the bimetallic Au/Ag nanoparticles from EDS and XPS analysis were 36 and 71 wt%, respectively, suggesting that bimetallic Au core/Ag shell structure was formed by competitive reduction of Au³⁺ and Ag+ ions with Persimmon leaf extract. This work was presented at 13 ^th YABEC symposium held at Seoul, Korea, October 20–22, 2007.     

Electrodeposition of Ag and Pd on a reconstructed Au(1 1 1) electrode surface studied by in situ scanning tunneling microscopy

Electrochemical deposition of Ag and potential-induced structural change of the deposited Ag layer on a reconstructed surface of Au(1 1 1) electrode were followed by in situ scanning tunneling microscope (STM). A uniform Ag monolayer was formed on a reconstructed Au(1 1 1) surface in a 50-mM H₂SO₄ solution at +0.3 V (vs. Ag/AgCl) after adding a solution containing Ag₂SO₄ so that the concentration of Ag⁺ in the STM cell became ca. 2 μM. No characteristic height corrugation such as the Au reconstruction was observed on the surface, indicating that the lifting of the substrate Au reconstruction occurred by Ag deposition. The formed Ag monolayer was converted to a net-like shaped Ag nano-pattern of biatomic height when the potential was stepped from +0.3 to −0.2 V in the solution containing 2 μM Ag⁺. This result indicates that the substrate Au(1 1 1)-(1 × 1) surface was converted to the reconstructed surface even in the presence of Ag adlayer. Quite different structure was observed for Pd deposition on a reconstructed surface of Au(1 1 1) electrode at +0.3 V and the origin for this difference between Ag and Pd deposition is discussed.     

XPS and EIS studies of sputtered Al–Ce films formed on AA6061 aluminum alloy in 3.5% NaCl solution

X-ray photoelectron spectroscopy (XPS) was used to analyze the composition of films at different deposition parameters of sputtered Al-Ce coatings on AA6061 aluminum alloys. By means of electrochemical impedance spectroscopy (EIS) measurements, the protective character of these coatings was studied for 21 days of exposure in a 3.5 wt% NaCl solution and an attempt was made to establish the relationship between film thickness and chemical composition (Al/Ce, Ce³/Ce⁴⁺ ratios) of the surface before and after the electrochemical characterization. XPS studies revealed the presence of the Al^o, Al₂O₃, CeO₂ and Ce₂O₃ compounds, confirming that the sputtered Al-Ce films were deposited in the metallic form and thereafter were superficially oxidized under ambient conditions. The Al–Ce bonds were overlapped with the signal of cerium oxides. The transport phenomena in the oxide film or controlled diffusion process are strongly dependent on the deposition parameters and exposure time in the aggressive medium. It was also found that in the deposited samples at p₄P₂₀₀t₃₀₀, the film was still present after 21 days of exposure, although with visible cracks and erosion areas; however, the Ce³/Ce⁴⁺ ratio almost remained constant before and after the electrochemical characterization, which explained the barrier properties of these samples as compared with others at different deposition parameters.     

Fabrication of a stable, switchable An/SAM-Au electrode with tunable electron transfer and excellent electrochemical properties

This paper describes the electrochemical properties, such as electrode reactivity, and interfacial capacitance of an anthracene/self-assembled monolayer (An/SAM) Au electrode prepared through controllable immersion of the dodecanethiol (C₁₂SH) SAM-Au electrode in a THF solution of anthracene (An). The C₁₂SH SAM almost totally blocks heterogeneous electron transfer between the bare Au electrode and Fe(CN)₆^3−/4− in solution, but adsorption of the An molecules onto the SAM-Au electrode restores electron transfer. The prepared An/SAM-Au electrode possesses good reactivity without a remarkable barrier to heterogeneous electron transfer. On the other hand, the electroactive form of the An/SAM-Au electrode can be converted back to the non-electroactive form by immersing the electrode into pure THF.     

Biomass grafted with polyamic acid for enhancement of cadmium(II) and lead(II) biosorption

In this study, a simple method was used to prepare modified biomass to improve its adsorption capacity for Cd²⁺ and Pb²⁺. The modified biomass of baker’s yeast was obtained by grafting polyamic acid, which was prepared via the reaction of pyromellitic dianhydride (PMDA) and lysine, onto the surface of glutaraldehyde-pretreated biomass at 50 °C for 3 h. The presence of polyamic acid on the biomass surface was verified by Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS), the morphologies of the biomass before and after modification were observed by microscope. Due to the high density of the carboxyl and amide groups on the biomass surface, the uptake for Cd²⁺ and Pb²⁺ showed a significant increase. According to Langmuir adsorption isotherm, the maximum uptake for Cd²⁺ and Pb²⁺ were 95.2 and 204.5 mg g⁻¹, which were 15- and 11-fold for that obtained on the uncontaminated biomass. The kinetics for Cd²⁺ and Pb²⁺ adsorption followed the pseudo-second-order model. The results of FTIR and XPS revealed that carboxyl, amide, and hydroxyl groups on the biomass surface were involved in the adsorption of Cd²⁺ and Pb²⁺.     

How Different Characterization Techniques Elucidate the Nature of the Gold Species in a Polycrystalline Au/TiO2 Catalyst

TiO₂‐supported gold species were prepared via the deposition‐precipitation route, with conservation of the initial speciation by freeze‐drying. The structural and electronic properties of the Au species were investigated by X‐ray absorption spectroscopy, electron microscopy, and IR spectroscopy of adsorbed CO in four states. Exclusively Au^III was deposited on the TiO₂ surface in patches ranging from isolated Au ions to three‐dimensional clusters. This paper illustrates in detail the unique contributions of all characterization techniques to this structural model.     

Selective formation of monodisperse CdSe nanoparticles on functionalized self-assembled monolayers using chemical bath deposition

Using CdSe chemical bath deposition (CBD) we demonstrate the selective growth and deposition of monodisperse nanoparticles on functionalized self-assembled monolayers (SAMs) using time-of-flight secondary ion mass spectrometry and scanning electron microscopy. We show that the deposition mechanism involves both ion-by-ion growth and cluster-by-cluster deposition. On -COOH terminated SAMs strongly adherent CdSe nanoparticles form via a mixed ion-by-ion and cluster-by-cluster mechanism. Initially, Cd²⁺ ions form complexes with the terminal carboxylate groups. The Cd²⁺-carboxylate complexes then act as the nucleation sites for the ion-by-ion growth of CdSe. After a sufficient concentration of Se²⁻ has formed in solution via the hydrolysis of selenosulfate ions, the deposition mechanism switches to cluster-by-cluster deposition. On -OH and -CH₃ terminated SAMs monodisperse CdSe nanoparticles are deposited via cluster-by-cluster deposition and they do not bind strongly to the surface. Finally, under the appropriate experimental conditions we demonstrate the selective deposition of CdSe nanoparticles on patterned -CH₃/-COOH SAMs.     

Self-assembly on copper surface by using imidazole derivative for corrosion protection

This paper presents the self-assembly of 1-(3-aminopropyl) imidazole (API) monolayer on the copper surface to study the inhibition effect of the API against copper corrosion in 3% NaCl solution. The optimum concentration and assembling time for the assembly of API on copper were ascertained using electrochemical impedance spectroscopy (EIS). It was found that the API self-assembled monolayer (SAM) was formed with the concentration of 1.0 mM of API at 24 h assembling time and the maximum inhibition efficiency that could be achieved was 93.10%. The API SAM on copper was characterized by Fourier transform infrared spectroscopy (FT-IR), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle measurement (WCA). The presence of N and C signals in the XPS and EDX, show that the API molecules successfully anchor on the copper surface which demonstrates formation of API SAM on the copper surface. Corrosion protection capability of the copper modified with API was evaluated by the electrochemical polarization study (EPS) and scanning electron microscopy (SEM). The results of electrochemical and SEM analysis revealed that the API modified copper showed better corrosion protection in 3% NaCl solution.