Synthesis of dendritic silver nanostructures and their application in hydrogen peroxide electroreduction

Well-defined silver (Ag) dendritic nanostructures were successfully synthesized by electrodeposition without the use of any template or surfactant. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to investigate the as-prepared Ag nanomaterials. These dendrites are aggregates of Ag nanoparticles, which are highly crystalline in nature. The concentration of AgNO₃ affects the shape of the nanoparticles. In addition, the electrochemical properties of the Ag dendrite-modified glassy carbon electrode (Ag/GC) were characterized by cyclic voltammetry and chronoamperometry. Results indicated that the as-obtained Ag dendrites exhibited favorable electroreduction activity towards oxygen (O₂) and hydrogen peroxide (H₂O₂). When used as a sensor, the Ag/GC electrode exhibited a wide linear range of 0.005–12 mM H₂O₂, with a remarkable sensitivity of 7.39 μA/mM, a detection limit of 0.5 μM, estimated at a signal-to-noise ratio of 3, and a rapid response time (within 5 s). Moreover, the electrode showed good reproducibility, anti-interferant ability and long-term stability.     

Macroporous silicon for high-capacitance devices using metal electrodes

In this paper, high-capacity energy storage devices based on macroporous silicon are demonstrated. Small footprint devices with large specific capacitances up to 100 nF/mm², and an absolute capacitance above 15 μF, have been successfully fabricated using standard microelectronics and MEMS techniques. The fabricated devices are suitable for high-density system integration. The use of 3-D silicon structures allows achieving a large surface to volume ratio. The macroporous silicon structures are fabricated by electrochemical etching of silicon. This technique allows creating large structures of tubes with either straight or modulated radial profiles in depth. Furthermore, a very large aspect ratio is possible with this fabrication method. Macroporous silicon grown this way permits well-controlled structure definition with excellent repeatability and surface quality. Additionally, structure geometry can be accurately controlled to meet designer specifications. Macroporous silicon is used as one of the electrodes over which a silicon dioxide insulating layer is grown. Several insulator thicknesses have been tested. The second capacitor electrode is a solid nickel filling of the pores prepared by electroplating in a low-temperature industry standard process. The use of high-conductivity materials allows reaching small equivalent series resistance near 1 Ω. Thanks to these improvements, the presented devices are capable of operating up to 10 kHz.

PACS

84.32.Tt; 81.15.Pq; 81.05.Rm     

Protective properties of cataphoretic epoxy coating on aluminium alloy AA6060 modified with electrodeposited Ce-based coatings: Effect of post-treatment

Ce-based conversion coatings (CeCCs) are a promising alternative to toxic chromate coatings on the metal substrates. In this work the CeCCs were electrodeposited on aluminium alloy AA6060 from aqueous solution of Ce(NO₃)₃ at different potentials (−0.95 V, −1.2 V and −1.4 V). Effect of deposition potential and post-treatment in the phosphate solution on morphology and protective properties of CeCCs with top cataphoretic epoxy coating was studied. To assess the differences between the protective systems, originating from the different CeCCs pre-treatments, electrochemical impedance spectroscopy (EIS), polarization measurements, AFM and SEM/EDS analysis were used. The EIS study was undertaken to follow the evolution of corrosion behaviour of epoxy coating/CeCCs protective systems over prolonged time of exposure to the chloride environment (3 wt.% NaCl). Results suggest significantly improved corrosion stability of epoxy coating on AA6060 with as-deposited CeCCs sub-layers with respect to the same epoxy coatings with phosphate post-treated CeCCs. The far best protective properties, i.e., the greatest value of pore resistance and the lowest value of corrosion current density were provided by the epoxy coating/CeCC protective system with CeCC deposited at −1.2 V and without post-treatment.     

Electrodeposited CuMnS and CoMnS electrodes for high-performance asymmetric supercapacitor devices

The transition metal sulfides have gained extensive interest in energy storage devices owing to their unique features. However, the research-based on cobalt, copper and manganese sulfide composites is limited while they are considered as promising contenders for supercapacitor electrodes. The simplest and facile one-step electrodeposition technique was adopted for the direct growth of CuMnS and CoMnS on a Ni-substrate. The electrochemical properties of CuMnS and CoMnS electrodes were investigated and maximum specific capacitances of 1691 and 2290 F/g, respectively, were obtained at 10 A/g current density. Further, these electrodes are investigated with activated carbon (AC) electrode to fabricate asymmetric supercapacitor devices where CoMnS//AC exhibited superior energy density values than CuMnS//AC device. However, both the devices show a relatively uniform capacitance retention rate (~94%) after 2500 charging-discharging cycles. Furthermore, the role of capacitive- and diffusive-controlled contributions in the charge storage phenomenon of supercapacitor devices are explicitly scrutinized by employing Dunn's model. Co-electrodeposition of transition metal sulfides has great potential as electrode material for highly effective supercapacitor devices.     

The effect of bioactive glass nanoparticles on corrosion barrier performance and bioactivity of zinc oxide coatings electrodeposited on Ti6Al4V substrate

Zinc oxide coatings were electrodeposited on Ti6Al4V substrates from a nitrate bath with and without 1 wt% BG nanoparticles at ?1.2 and ?1.4 V_Ag/AgCl, where the former voltage created a spherical morphology, the latter developed a flower-like one. The spherical morphology was modified through the incorporation of BG nanoparticles, where surface roughness, wettability, and adhesion strength of the coating were enhanced. The coatings with spherical morphology also revealed complete barrier property after immersion in PBS solution. However, fully adverse effects were found for the coatings deposited at ?1.4 V_Ag/AgCl. This indicates that morphology is the most important factor determining the properties of ZnO and ZnO-BG coatings. The highest corrosion barrier performance was achieved for the ZnO-BG composite coating with spherical morphology. Although the composite coating with flower-like morphology did not provide complete barrier property at short immersion times, it earned that at longer times due to the plugging supported by the BG nanoparticles. The bioactivity tests in SBF at long times showed that the formation of Ca-P deposits on the surface of the composite coatings was noticeably improved.     

Characterization of electrodeposited WO3 films and its application to electrochemical wastewater treatment

WO₃ films have been prepared on to IrO₂-coated Ti substrate by cathodic deposition, and as-deposited and annealed films have been characterized using XRD, TEM, Raman and FT-IR spectroscopy. The as-deposited film consists of nanocrystalline, orthorhombic WO₃·H₂O and this phase transforms to amorphous WO₃ by annealing at 250 °C and to monoclinic WO₃ by annealing at and above 350 °C. The as-deposited and annealed films have been used as anodes for electrochemical decomposition of phenol in aqueous solutions with and without chloride ions. The monoclinic WO₃ anodes prepared by annealing at 350 and 400 °C show relatively high electrochemical activity in the chloride-containing solution. In addition, the anodes possess high chemical and physical stabilities: very low dissolution rate of WO₃ during the electrolysis and good adhesion to the substrate. Thus, WO₃ anodes may be promising materials for anodic oxidation of bio-refractory organics in wastewater, although further improvement of electrochemical activity is needed for more effective decrease in total organic carbons in wastewater.     

Electrodeposition of silver telluride thin films from non-aqueous baths

We describe a method for preparation of crystalline silver telluride films by cathodic deposition from dimethyl sulfoxide (DMSO) solutions containing 0.1 M NaNO₃, 5.0 mM AgNO₃ and 3.5-7.0 mM TeCl₄. X-ray diffraction data indicated that the deposited silver telluride films could be adjusted from Ag excess and stoichiometric monoclinic Ag₂Te to hexagonal Ag₇Te₄ by increasing the concentration of TeCl₄ in the electrolyte or lowering the deposition potential. The Ag₂Te film is gray and the Ag₇Te₄ film is dark blue-gray and mirror like adhered strongly to the substrates. Scanning electron microscopy images show that Ag₂Te films were formed with globular grains with average diameters of more than 1 μm. In contrast, Ag₇Te₄ film consists of triangles characteristic of a (1 1 1) single-crystal with a hexagonal structure in average sizes of about 0.4 μm. The X-ray photoelectron spectra (XPS) indicated that the binding energies deviation of Te3d in Ag₇Te₄ is less than that in Ag₂Te, which is consistent with the apparent valences of Te in Ag₂Te and Ag₇Te₄. Finally, the cathodic deposition reactions were studied by cyclic voltammetry.     

Electrodeposition of PtZn in a Lewis acidic ZnCl2-1-ethyl-3-methylimidazolium chloride ionic liquid

The electrodeposition of PtZn from a Lewis acidic 40-60 mol% zinc chloride-1-ethyl-3-methylimidazolium chloride ionic liquid containing PtCl₂ was investigated at polycrystalline tungsten substrates at 90 °C. Cyclic voltammetric data indicates that Pt(II) was reduced at a potential slightly more positive than Zn(II) was. The Pt-Zn electrodeposits exhibited multiple anodic stripping waves. The Zn-dominant deposits were stripped at a potential less positive than that of the Pt-dominant deposits. Energy-dispersive spectroscopy and scanning electron microscopy data indicated that the composition and morphology of the electrodeposited Pt-Zn alloys were affected by the deposition potential and the Pt(II) concentration in the plating solution. The electrodeposition of Zn at a Pt substrate also produced surface Pt-Zn alloys. The Pt of the electrochemically prepared Pt-Zn alloys was easier to oxidize than the bulk Pt substrate.     

Cr2O3 nanoparticles: A promising candidate to improve the mechanical properties and corrosion resistance of Ni-Co alloy coatings

This study was aimed to assess the effects of reinforcement nanoparticles content, on the microstructural features, mechanical properties, and corrosion-related properties of Ni-Co-Cr₂O₃ nanocomposite coatings. Scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDS), and X-ray diffraction (XRD) analysis were employed in order to evaluate the microstructural features and chemical composition of the nanocomposites. Moreover, the microhardness tester and electrochemical impedance spectra (EIS) tests coupled with potentiodynamic polarization measurements were used to investigate the mechanical and corrosion-related properties, respectively. Results demonstrate that albeit the volume fraction of cobalt in coating, average particle size, Cr₂O₃ nanoparticle content in coating, and microstructural features are of prime significance in determining the mentioned properties of the nanocomposite coatings, Co content is more important. Actually, Cr₂O₃ nanoparticles serve as suitable nucleation sites for Co particles deposition throughout the microstructure. Thus, combined actions of Cr₂O₃ nanoparticles incorporation and their optimal content ensures the nucleation of high population of Co particles, which significantly contributes to the improvement in the properties. The Ni-Co-8.9 wt%Cr₂O₃ nanocomposite coating exhibits the superior mechanical and corrosion-related properties.     

Electrochemical and spontaneous deposition of ruthenium at platinum electrodes for methanol oxidation: an electrochemical quartz crystal microbalance study

PtRu electrodes with Ru surface concentration ranging from 20 to 50% were prepared by electrolysis of Ru(NO)(NO₃)₃ at a constant potential and/or by spontaneous Ru deposition performed at open circuit potential from a RuCl₃ solution. The amount of either spontaneously or electrochemically deposited ruthenium on the platinum electrode was determined by means of an electrochemical quartz crystal microbalance (EQCM). The effect of the Ru surface concentration on the rate of methanol electrooxidation was also investigated and correlated to the EQCM measurements.