Electrochemical characterization of the underpotential deposition of tellurium on Au electrode

Electrochemical characterization of the underpotential deposition (UPD) of tellurium on Au substrate has been performed in this paper. The mechanism of Te deposition and its voltammetry dependence on the Te ion concentration were studied, and it suggests that variations in the metal ion concentration may affect the UPD process kinetics. The effect of tellurium adsorbates on UPD behavior of Te has also been investigated. The results show that the tellurium adsorbates could be irreversibly adsorbed upon the Au substrate surface under the open-circuit conditions. Subsequent removal of the Te adsorbates was also proved to be very difficult within the Au double-layer region, and a standard electrochemical cleaning procedure is necessary to remove the Te adsorbates completely. When the potential was cycled into the Au oxidation region, a substantial loss of Te adsobates was observed, which occurs simultaneously with the Au oxidation features. Scan rate dependent cyclic voltammetry experiments reveal that the peak current in the Te UPD peak is not a linear function of the scan rate, ν, but of a 2/3 power of the scan rate, ν^2/3. It is in good consistent with a two-dimension nucleation and growth mechanism.     

Synthesis,optical and electrochemical properties of ZnO nanowires/graphene oxide heterostructures

Large-scale vertically aligned ZnO nanowires with high crystal qualities were fabricated on thin graphene oxide films via a low temperature hydrothermal method. Room temperature photoluminescence results show that the ultraviolet emission of nanowires grown on graphene oxide films was greatly enhanced and the defect-related visible emission was suppressed, which can be attributed to the improved crystal quality and possible electron transfer between ZnO and graphene oxide. Electrochemical property measurement results demonstrated that the ZnO nanowires/graphene oxide have large integral area of cyclic voltammetry loop, indicating that such heterostructure is promising for application in supercapacitors.     

Fabrication of diameter-modulated and ultrathin porous nanowires in anodic aluminum oxide templates

Anodic aluminum oxide (AAO) membranes with modulated pore diameter were synthesized by pulse anodization in 0.3 M sulfuric acid at 1 °C. For AAO growth, a typical combination of alternating mild anodizing (MA) and hard anodizing (HA) pulses with applied potential pulses of 25 V and 35 V was applied. The control of the duration of HA pulses will provide an interesting way to tune the shape of pores and the structure of AAO channels. It was found that a non-uniform length of HA segments in cross section of AAO is usually observed when the HA pulse duration is shorter than 1.2 s. The pulse anodization performed with longer HA pulses leads to the formation of AAO templates with periodically modulated pore diameter and nearly uniform length of segments. Various diameter-modulated metallic nanowires (Au, Ag, Ni and Ag–Au) were fabricated by electrodeposition in the pores of anodic alumina membranes. A typical average nanowire diameter was about 30 nm and 48 nm for MA and HA nanowire segments, respectively. After a successful dealloying silver from Ag–Au nanowires, porous ultrathin Au nanowires were obtained.     

Solvothermal synthesis of CdS nanowires templated by polyethylene glycol

CdS nanowires were solvothermally synthesized from Cd(NO₃)₂ and S powder using ethylenediamine as a solvent and polyethylene glycol (PEG) as a template. Hexagonal CdS with P6₃mc space group was detected using XRD and SAED, results which are in good accordance with those obtained by the simulation. SEM, TEM and HRTEM revealed the gradual development of nanowires in the [0 0 1] direction with a number of atoms aligning in a crystal lattice. Raman spectra of different products showed the fundamental and overtone modes at the same wavenumbers of 300 and 601 cm⁻¹, respectively. Their relative intensities at different molecular weight PEG were influenced by the anisotropic geometry of the products. Their photoluminescence peaks were detected at the same wavelengths of 518 nm. A formation mechanism for CdS nanowires was also proposed to relate to the experimental results.     

Electrochemical studies of Zn underpotential/overpotential deposition on a nickel electrode from non-cyanide alkaline solution containing glycine

In this work we present an electrochemical study of the underpotential deposition (UPD) and overpotential deposition (OPD) of zinc onto nickel electrode (NE) from a non-cyanide alkaline solution containing glycine. The studied parameters were zinc concentration, glycine concentration and scanning rate. The analysis of the experimental data clearly showed the presence of UPD and OPD processes that started at −0.8 V vs. SCE and −1.4 V vs. SCE, respectively. The voltammetric studies also indicate diffusion control of the zinc UPD and OPD processes onto the NE. From the potentiostatic transients we found instantaneous nucleation (2D) mechanisms, which agree to that observed in the AFM study. In order to compare the effect of zinc/glycine concentration, we calculate thermodynamic parameters for the OPD process.     

The underpotential deposition of bismuth and tellurium on cold rolled silver substrate by ECALE

Thin-layer electrochemical studies of the underpotential deposition (UPD) of Bi and Te on cold rolled silver substrate have been performed. Different approaches have been employed to investigate the influence of silver oxide film on Bi UPD. As a result, the precedent deposition of a little bismuth can effectively prevent silver from surface oxidation. The voltammetric analysis of underpotential shift demonstrates that the first Te UPD on Bi-covered Ag and Bi UPD on Te-covered Ag fit UPD dynamics mechanism. Thin film of bismuth telluride was formed using an automated flow deposition system, by alternately depositing Te and Bi. The electrochemical conditions necessary to form Bi₂Te₃ deposits of 50 cycles on cold rolled silver by ECALE are described here. X-ray diffraction indicated the deposits were Bi₂Te₃. EDX quantitative analysis gave the 2:3 stoichiometric ratio of Bi to Te, which is consistent with XRD result. Electron probe microanalysis of the deposits showed a worm-like network structure. The map of Te and Bi element indicated the distribution of both Te and Bi is homogeneous and locates the same sites, which is favorable to Te-Bi binary system. The composition analysis of structural expanded image also showed the approximately constant composition of Te:Bi ≈ 3:2 has taken place.     

Photoluminescence of poly(thiophene) nanowires confined in porous anodic alumina membrane

Poly[3-(2-methoxyphenyl)thiophene] (PMP-Th) nanowires confined in the nano-channels of porous anodic alumina (PAA) membranes were first prepared through electrochemical deposition in cyclic voltammetry and investigated by photoluminescence (PL) spectroscopy. The morphologies and molecular structures of PMP-Th/PAA nanocomposites were studied with electron microscopy and FT-IR. The maximum absorption in UV–vis spectrum of the PMP-Th/PAA nanocomposites was located at 400–450 nm. The photoluminescence spectra show that the nanocomposites have green luminescence bands with the peaks at 560–570 nm. Compared to the electropolymerized PMP-Th film, the PMP-Th nanowires confined in the nano-channels of PAA membranes exhibit obvious blue-shifts in luminescent spectra and great enhancements in photoluminescence intensity. Further spectral analyses suggest that the PL enhancement could be attributed to Förster energy transfer from oxygen vacancies in PAA to PMP-Th molecules.     

Thiourea assisted one-pot easy synthesis of CdS/rGO composite by the wet chemical method: Structural,optical, and photocatalytic properties

We report on the synthesis of CdS/reduced graphene oxide (rGO) composite by a wet chemical method. Thiourea was used both as a sulfur source and as a reducing agent to convert graphene oxide to rGO. The structural and morphological confirmation for the reduction of graphene oxide and the formation of the CdS/rGO composite was demonstrated by X-ray diffractometry, Raman spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses. Photoluminescence spectra of the composite exhibited a more efficient luminescence quenching in comparison with pure CdS nanoparticles. The composite demonstrated 99% photodegradation of methyl orange under UV irradiation, which is much superior than the photodegradation of methyl orange under similar conditions exhibited by CdS nanoparticles (72%).     

Straightening of chemically deposited CdS nanowires through annealing towards improved PV device performance

Cadmium sulfide (CdS) thin film consisting of nanowires over a flat CdS thin film were synthesized by depositing cadmium hydroxide [Cd(OH)₂] nanowires (NW) bundles, followed by conversion to sulfide phase by using ion exchange route at room temperature (300 K) based on negative free energy of formation. The influence of post annealing treatment on as-deposited CdS NW films has been studied in the temperature range 423–523 K through the observation of nanowires alignments. The annealing effect on the intrinsic properties have been studied in relation with the crystallites sizes, micro strain, dislocation density and optical band gap of the deposited films. Furthermore, the behavior of inter- and intramolecular hydroxide ion (OH⁻) has been investigated from FTIR analysis. Additionally, the effects of post annealing on photovoltaic device performance has been scrutinized and the obtained results were correlated with structural and optical properties.     

An alternative route for the synthesis of silicon nanowires via porous anodic alumina masks

Amorphous Si nanowires have been directly synthesized by a thermal processing of Si substrates. This method involves the deposition of an anodic aluminum oxide mask on a crystalline Si (100) substrate. Fe, Au, and Pt thin films with thicknesses of ca. 30 nm deposited on the anodic aluminum oxide-Si substrates have been used as catalysts. During the thermal treatment of the samples, thin films of the metal catalysts are transformed in small nanoparticles incorporated within the pore structure of the anodic aluminum oxide mask, directly in contact with the Si substrate. These homogeneously distributed metal nanoparticles are responsible for the growth of Si nanowires with regular diameter by a simple heating process at 800°C in an Ar-H₂ atmosphere and without an additional Si source. The synthesized Si nanowires have been characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman.     

Electrochemical properties of N-doped hydrogenated amorphous carbon films fabricated by plasma-enhanced chemical vapor deposition methods

Nitrogen-doped hydrogenated amorphous carbon thin films (a-C:N:H, N-doped DLC) were synthesized with microwave-assisted plasma-enhanced chemical vapor deposition widely used for DLC coating such as the inner surface of PET bottles. The electrochemical properties of N-doped DLC surfaces that can be useful in the application as an electrochemical sensor were investigated. N-doped DLC was easily fabricated using the vapor of nitrogen contained hydrocarbon as carbon and nitrogen source. A N/C ratio of resulting N-doped DLC films was 0.08 and atomic ratio of sp³/sp²-bonded carbons was 25/75. The electrical resistivity and optical gap were 0.695 Ω cm and 0.38 eV, respectively. N-doped DLC thin film was found to be an ideal polarizable electrode material with physical stability and chemical inertness. The film has a wide working potential range over 3 V, low double-layer capacitance, and high resistance to electrochemically induced corrosion in strong acid media, which were the same level as those for boron-doped diamond (BDD). The charge transfer rates for the inorganic redox species, Fe^2+/3+ and Fe(CN)₆^4−/3− at N-doped DLC were sufficiently high. The redox reaction of Ce^2+/3+ with standard potential higher than H₂O/O₂ were observed due to the wider potential window. At N-doped DLC, the change of the kinetics of Fe(CN)₆^3−/4− by surface oxidation is different from that at BDD. The rate of Fe(CN)₆^3−/4− was not varied before and after oxidative treatment on N-doped DLC includes sp² carbons, which indicates high durability of the electrochemical activity against surface oxidation.     

Electrochemical synthesis and optical properties of helical polyaniline nanofibers

Helical polyaniline (PANI) nanofibers were facilely synthesized via a direct electrochemical method without using any template in the presence of (1S)-(+)-camphor-10-sulfonic acid (d-CSA) or (1R)-(−)-camphor-10-sulfonic acid (l-CSA) as the dopant. The helical morphologies of the PANI nanofibers prepared from potentiostatic deposition were confirmed with SEM and TEM. The helical PANI nanofibers induced by d-CSA and l-CSA exhibited mirror-imaged circular dichroism spectra in the UV-vis range, indicating the stereochemical selectivity of the electrochemical polymerization. The colors and optical activities of these nanofibers can be maintained on an indium-tin oxide (ITO) coated electrode with a dedoping/redoping treatment. The optical activities of the helical PANI nanofibers reversibly varied with different oxidized forms, which were easily controlled by the different potentials applied to the nanofibers.     

Synthesis of ZnO nanowires on Si substrate by thermal evaporation method without catalyst: Structural and optical properties

Synthesis of ZnO nanowires was achieved on Si(100) substrate by the thermal evaporation of high purity metallic zinc powder without the use of any metal catalyst or additives. The diameter and length of the as-grown nanowires were in the range of 20–35 nm and few micrometers, respectively. The shapes and sizes of ZnO nanowires were dependent on the growth time. The high resolution transmission electron microscopy and selected area electron diffraction patterns indicated that the as-grown products are single crystalline with wurtzite hexagonal phase. Room temperature photoluminescence studies exhibited a strong UV emission and a suppressed green emission, confirming the good optical properties for the deposited nanowires.     

Effect of Gd doping on structural,optical properties,photoluminescence and electrical characteristics of CdS nanoparticles for optoelectronics

Synthesis of pure and 0.1 to 5?wt.% Gd-doped CdS nanoparticles (NPs) was achieved through a modified domestic microwave-assisted route in a short timespan at 700?W power. The formation of hexagonal CdS NPs was verified via X-ray diffraction analysis, and no structural variation was observed except for lattice variation. The size of the crystallites (D), dislocation concentration, and lattice strain were calculated, and the D was in the range of 3–6?nm. Fourier transform-Raman analysis confirmed the presence of 1LO, 2LO, and 3LO modes at 294.76, 590, and 890?cm^?1, respectively, in all the synthesized nanostructures, with minute variations in their positions due to doping; however, no new mode was observed. The position of the vibration modes was red shifted compared to that of the bulk material, indicating a confinement effect. Scanning electron microscopy (SEM) mapping/energy-dispersive X-ray spectroscopy revealed homogeneous doping of Gd and the presence of all the constituents in the final products. The morphology of the synthesized materials was tested via field-emission SEM, which revealed spherical NPs with small dimensions. Additionally, high-resolution transmission electron microscopy was performed to visualize the shape and size of the prepared 0.1% Gd:CdS NPs. The energy gap was calculated using the Kubelka–Munk theory and found to be in the range of 2.31–2.41?eV. The photoluminescence emission spectra exhibited two green emission peaks at 516?±?2?nm and 555?±?2?nm and showed the reduction of defects with Gd doping in terms of intensity quenching. The dielectric constant (${\epsilon }^{\text{'}}$), loss, and alternating-current electrical properties were studied in the high-frequency range. The values of ${\epsilon }^{\text{'}}$ were in the range of 17–27. An enhancement of these values was observed for CdS when it was doped with Gd. The electrical conductivity exhibited frequency power law behavior.     

Fabrication of cobalt-nickel binary nanowires in a highly ordered alumina template via AC electrodeposition

Cobalt-nickel (Co-Ni) binary alloy nanowires of different compositions were co-deposited in the nanopores of highly ordered anodic aluminum oxide (AAO) templates from a single sulfate bath using alternating current (AC) electrodeposition. AC electrodeposition was accomplished without modifying or removing the barrier layer. Field emission scanning electron microscope was used to study the morphology of templates and alloy nanowires. Energy-dispersive X-ray analysis confirmed the deposition of Co-Ni alloy nanowires in the AAO templates. Average diameter of the alloy nanowires was approximately 40 nm which is equal to the diameter of nanopore. X-ray diffraction analysis showed that the alloy nanowires consisted of both hexagonal close-packed and face-centered cubic phases. Magnetic measurements showed that the easy x-axis of magnetization is parallel to the nanowires with coercivity of approximately 706 Oe. AC electrodeposition is very simple, fast, and is useful for the homogenous deposition of various secondary nanostuctured materials into the nanopores of AAO.     

Electrochemical synthesis of poly(p-phenylene) and poly(p-phenylene)/TiO2 nanowires in an ionic liquid

This study shows for the first time that poly(p-phenylene) (PPP) nanowires can be easily obtained by electrochemical synthesis at room temperature. The method involves the template assisted electropolymerization of benzene in the air and water stable ionic liquid 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIm]FAP). Track-etched polycarbonate membranes (PC) with an average pore diameter of 90 nm were used as templates. Dense and highly flexible bundles of PPP nanowires with a high aspect ratio (>160) were easily obtained by this method. In addition, we present here our first results to obtain PPP/TiO₂ nanowires by the combination of a sol–gel technique with electropolymerization. HR-SEM, TEM and EDX were used for the structural characterization of the nanowires.     

Physical and electrochemical characterization of CdS hollow microspheres prepared by a novel template free solution phase method

Novel CdS hollow microspheres have been successfully synthesized via a facile template-free solution-phase reaction from cadmium nitrate and thioacetamide precursors. The morphology of CdS hollow microspheres depends strongly on the ratio between the precursors, cadmium nitrate to thioacetamide ratio. The physical properties of the hollow microspheres have systematically been studied by different characterization methods. The stoichiometry of the hollow microspheres studied by the energy dispersive X-ray diffraction spectroscopy confirmed that the synthesized CdS hollow microspheres are nearly stoichiometric bulk like CdS. The morphology of the hollow microspheres studied by high resolution scanning electron microscopy and transmission electron microscopy observations showed that the CdS hollow microspheres of the size of 2.5 μm have hollow structure and are constructed by several nanoparticles of the size between 30 and 40 nm. The UV-visible diffuse reflectance spectroscopy studies showed that the band gap of the CdS hollow microspheres increased while increasing the cadmium nitrate to thioacetamide ratio. Further electrochemical characterization of CdS hollow microspheres was performed with glassy carbon electrode (GCE) after its chemical modification by CdS dispersed in dimethylformamide. The electrochemical studies showed that with decreasing the band gap energy the electron transfer resistance of CdS/GCE was also found decreased. Moreover, electrochemical impedance spectroscopic measurements showed enhanced DNA adsorption onto CdS/GCE in comparison to GCE. These experiments demonstrate that the CdS hollow microspheres act as an efficient electrode modifier that effectively decreased the charge transfer resistance and capacitance of the modified sensors, which can be used for electroanalytical purposes.     

Electroplating and magnetostructural characterization of multisegmented Co54Ni46/Co85Ni15 nanowires from single electrochemical bath in anodic alumina templates

Highly hexagonally ordered hard anodic aluminum oxide membranes, which have been modified by a thin cover layer of SiO₂ deposited by atomic layer deposition method, were used as templates for the synthesis of electrodeposited magnetic Co-Ni nanowire arrays having diameters of around 180 to 200 nm and made of tens of segments with alternating compositions of Co₅₄Ni₄₆ and Co₈₅Ni₁₅. Each Co-Ni single segment has a mean length of around 290 nm for the Co₅₄Ni₄₆ alloy, whereas the length of the Co₈₅Ni₁₅ segments was around 430 nm. The composition and crystalline structure of each Co-Ni nanowire segment were determined by transmission electron microscopy and selected area electron diffraction techniques. The employed single-bath electrochemical nanowire growth method allows for tuning both the composition and crystalline structure of each individual Co-Ni segment. The room temperature magnetic behavior of the multisegmented Co-Ni nanowire arrays is also studied and correlated with their structural and morphological properties.     

Strengthened porous alumina membrane tube prepared by means of internal anodic oxidation

A method for preparing an anodic aluminum oxide tube with a much higher mechanical strength than before was developed, where anodic oxidation was carried out from the inside of an aluminum tube (internal anodizing method). It was considered that the internal stress remaining in the alumina layer, which was formed in the course of the internal anodizing, resulted in a considerable improvement of compressive strength against external pressure. As a matter of fact, the tube could withstand at least up to 0.98 MPa of transmembrane pressure, which corresponded to 32.6 MPa in terms of breaking pressure. The tubular alumina membrane obtained had straight mesopores of 20–25 nm in diameter and, therefore, showed the Knudsen permselectivity for inorganic gases. Such a strengthened alumina tube is expected to be used as a porous membrane or as a support for composite membranes.