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A nanostructured electrochemical sensor of hydrogen peroxide was fabricated growing self-standing Pd nanowires (Pd NWs) into polycarbonate (PC) membranes through a simple metal galvanic deposition. Conditions of deposition were adjusted in order to attain 2–5 μm long Pd wires. Characterization of Pd-NWs was performed by scanning electrode microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Properties of the nanostructured sensor were studied by cyclic voltammetry and chronoamperometry in phosphate buffer—ethanol solution. Addition of pure ethanol to the test solution was essential in order to increase wettability of the nanostructures. Sensing features were compared with those of both compact and nanoparticle film. Results show stable behavior and sensitive response of Pd NWs towards H 2 O 2 with a wide linear dependence over H 2 O 2 concentration for the electrodes consisting of long Pd nanowires/nanotubes, which display an increase of sensitivity and lower limit of detection (LOD) in comparison with the other sensors. Also the linear-response interval widens with electrode specific surface area. Accuracy and selectivity (towards different electroactive species) is excellent.

In this work, the galvanic deposition method is used to deposit coatings of brushite/hydroxyapatite/polyvinyl acetate on 304 stainless steel. Coatings are obtained at different temperatures and with different sacrificial anodes, consisting of a mixture of brushite and hydroxyapatite. Samples are aged in a simulated body fluid (SBF), where a complete conversion of brushite into hydroxyapatite with a simultaneous change in morphology and wettability occurred. The corrosion tests show that, compared with bare 304, the coating shifts Ecorr to anodic values and reduces icorr Ecorr, and icorr has different values at different aging times due to chemical interactions at the solid/liquid interface. The best performing deposits are those obtained by using Al as the sacrificial anode. The metal ion release, measured after 21 days of aging, is very low and is attributable to the presence of a coating that slows the steel corrosion. Coating cytotoxicity is investigated through cell viability assays with MC3T3-E1 osteoblastic cells. The results reveal a high cytocompatibility comparable to that of a pure cell culture medium.

AgSe based nanostructures (nanowires or nanotubes) were obtained by electrodeposition. A systematic investigation was carried out, varying concentration of the precursors, pH of the electrolytic solution, ligands, and deposition mode, to study the effect of all these parameters on the growth of nanostructures. Nanostructure morphology depends also on the type of metal that was used as support, due to the secondary reaction of hydrogen evolution. On Ni support, the H2 evolution reaction led to formation of only nanotubes, while on copper substrate also nanowires were obtained. Composition of nanostructures depends strongly on solution pH. X-ray diffraction and Raman spectroscopy showed that in thiocyanate-free bath nanostructures consist in orthorhombic Ag2Se and metallic Ag. At higher pH values, the metallic Ag phase increased and the co-deposition of Se also occurred. We also found that the use of a thiocyanate bath with a specific composition permits to obtain nanostructures of pure orthorhombic Ag2Se.

Nanostructured Ni–IrO2 electrodes were fabricated by electrodeposition in a two-step procedure: first arrays of nickel nanowires (NWs) were electrodeposited within pores of polycarbonate (PC) membranes, then iridium oxide nanoparticles were deposited on the Ni metal after membrane dissolution, for improving the catalytic activity. The aim was to compare performance of these electrodes with traditional ones consisting of Ni film. Different methods of deposition of the IrO2 electrocatalyst were investigated and the effect on electrodes stability and activity is discussed. Despite a low coverage of Ni NWs by the electrocatalyst, results indicate a faster kinetics of O2 evolution in 1 M KOH solution and an improvement of performances for electrolysers having a nanostructured anode.

Electrochemical deposition of SnCo alloys inside the nanometric pores of commercial membranes is described. Composition, morphology and crystallographic structure of the synthesized nanostructured alloys are reported as well as the results of electrochemical tests carried out both in half-cell and in full battery configuration to investigate the performance of these SnCo alloys as anodes for lithium-ion batteries. Optimized depositions yielded nanostructured alloys that performed 200 deep galvanostatic cycles at C/2 and 30 °C with 80 % capacity retention and coulombic efficiency higher than 97 % after 40 cycles Moreover, charge-discharge rate capability tests showed the high performance of these SnCo alloys at high C-rate such as 10C. Tests of SnCo alloys in battery configuration against LiFePO4 cathode are also reported.

Very thin and uniform layers of indium sulfide were deposited on nickel nano-rods using the sequential and cyclical Spray-ILGAR® (Ion Layer Gas Reaction) technique. Substrates were fabricated by electrodeposition of Ni within the pores of polycarbonate membranes and subsequent chemical dissolution of the template. With respect to the depositions on flat substrates, experimental conditions were modified and optimized for the present geometry. Our results show that nano-rods up to a length of 10 μm were covered uniformly along their full length and with an almost constant film growth rate, thus allowing a good control of the coating thickness; the effect of the deposition temperature was also investigated. However, for high numbers of process steps, i.e. thickness, the films became uneven and crusty, especially at higher temperature, mainly owing to the simultaneous side reaction of the metallic Ni forming nickel sulfide at the surface of the rods. However, such a problem occurs only in the case of reactive nano-rod materials, such as less noble metals. It could be strongly reduced by doubling the spray step duration and thereby sealing the metallic surface before the process step of the sulfurization. Thus, quite smooth, about 100 nm thick coatings could be obtained.

In this work, brushite and brushite/hydroxyapatite (BS, CaHPO4·H2O; HA, Ca10(PO4)6(OH)2) coatings were deposited on 316L stainless steel (316LSS) from a solution containing Ca(NO3)2·4H2O and NH4H2PO4 by a displacement reaction based on a galvanic contact, where zinc acts as sacrificial anode. Driving force for the cementation reaction arises from the difference in the electrochemical standard potentials of two different metallic materials (316LSS and Zn) immersed in an electrolyte, so forming a galvanic contact leading to the deposition of BS/HA on nobler metal. We found that temperature and deposition time affect coating features (morphology, structure, and composition). Deposits were characterized by means of several techniques. The morphology was investigated by scanning electron microscopy, the elemental composition was obtained by X-ray energy dispersive spectroscopy, whilst the structure was identified by Raman spectroscopy and X-ray diffraction. BS was deposited at all investigated temperatures covering the 316LSS surface. At low and moderate temperature, BS coatings were compact, uniform and with good crystalline degree. On BS layers, HA crystals were obtained at 50 °C for all deposition times, while at 25 °C, its presence was revealed only after long deposition time. Electrochemical studies show remarkable improvement in corrosion resistance.

This work shows that it is possible to obtain self-standing Pd nanowires into anodic alumina membranes by a simple metal displacement deposition. By using a proper arrangement, specifically designed in order to optimize the process, polycrystalline Pd nanowires were deposited from a solution containing Pd(NH3)4(NO3)2 as precursor. Morphological analysis showed the formation of perfectly aligned nanowires with a uniform diameter throughout the entire length. This last parameter was controlled by both the deposition time and the ratio between the anodic area (active metal) and the cathodic area (pore bottom). Keywords: Displacement deposition, Template synthesis, Palladium nanowires, Alumina membranes

The anodic behaviour of cast Ti–Mo alloys, having different Mo contents (6–20 wt.%), was investigated in acidic and neutral aerated aqueous solutions. All sample showed a valve-metal behaviour, owing to formation and thickening of barrier-type anodic oxides displaying interference colours. Growth kinetics of passive films is influenced by both anodizing electrolyte and composition of the starting alloy. This last parameter was found to change also the solid-state properties of the films, explored by photoelectrochemical and impedance spectroscopy experiments. Thicker films ( U f = 8 V/MSE) grown on alloys richer in Mo showed more resistive character and a photocurrent sign inversion under negative bias, that revealed an insulating character, whereas corresponding films grown on alloys with lower Mo content, as well as thinner films, behaved as n-type semiconductors. Results are discussed in terms of formation of a mixed Ti–Mo oxide phase.

Different Ni nanostructure arrays were fabricated by pulsed electrodeposition from a Watts bath inside the pores of anodic alumina membrane (AAM) templates. Under a trapezoidal waveform of potential, consisting of fast linear sweeps between 0 and −3 V (SCE) interleaved by delay times at 0 (10 s) and −3 V (0.1 s), Ni nanowires were grown. The rate of nanowires growth was constant up to 60 min of deposition. For longer times, the growth of nanowires was not uniform, and after about 180 min some nanowires reached the template surface exposed to the electrolyte. Under square potential pulses between the same potentials (pulse length 1 s), nanotubes of Ni are obtained. Morphological analysis of these nanostructures at different lengths revealed that the inner profile of nanotubes evolved from cylindrical to conical with increasing deposition time. The possibility to grow either nanowires or nanotubes in dependence of the potential waveform, as well as the growth rate of nanostructures were discussed taking into account the reaction of hydrogen evolution, occurring simultaneously with Ni electrodeposition.

The influence of experimental parameters on the morphology of the porous structure and on the formation kinetics has been investigated for anodic alumina membranes (AAM) grown in aqueous H 3 PO 4 at 160 V. It was found that pore aspect ratio and membrane porosity on the solution-side surface are influenced by tensiostatic charge, bath temperature and the presence of Al 3+ ions in solution. Morphological and kinetic data, recorded in different conditions, give useful information on the growth mechanism of pore channels in phosphoric acid solution. Nickel nano-structures have been fabricated using AAM as template. Electroless deposition, performed by adding the reducing agent to a suitable bath in several steps, resulted in the formation of short metal nanotubes (about 5 μm long) in the upper part of the channels. Long Ni nanowires (up to 25 μm) with aspect ratio higher than 100 were obtained by pulsed unipolar electrodeposition from a Watt bath. In this case, both the influence of some experimental parameters on the nanowires growth and the fast current transients during the electrodeposition steps were analyzed.

A novel electrically conductive composite material, consisting of polyaniline (PANI) nanoparticles dispersed in a polyvinyl pyrrolidone (PVP) hydrogel, was prepared ‘in situ’ by water dispersion polymerisation (DP) of aniline using PVP as steric stabiliser, followed by γ-irradiation induced crosslinking of the PVP component. Conversion yield of aniline into PANI particles was determined via HPLC and gas chromatography, while structural confirmation of the synthesised polymer was sought by FTIR. Morphology and dimensions of PANI particles into the coloured, optically transparent hydrogel was determined by electronic microscopy; moreover, swelling behaviour of composite hydrogels in different buffer solutions was investigated by gravimetric measurements and compared to that of pure PVP hydrogels. Cyclic voltammetry experiments were carried out both on these hydrogels and on the parent aqueous dispersions, at different pH values of the suspending/swelling medium, while conductivity of the composite hydrogels was derived from Impedance Spectroscopy; in both cases results were compared to those relative to hydrogels containing commercial-grade PANI particles.

The anodic behaviour of two titanium cast alloys, obtained by fusion in a voltaic arc under argon atmosphere, was analyzed in aerated aqueous solutions having different pH values. In all solutions the alloys, having nominal compositions Ti–50Zr at.% and Ti–13Zr–13Nb wt.%, displayed a valve-metal behaviour, owing to the formation of barrier-type oxide films. Passive films, grown potentiodynamically up to about 9 V, were investigated by photocurrent spectroscopy (PCS) and electrochemical impedance spectroscopy (EIS). These passive layers show photoactivity under anodic polarizations, with optical gaps close to 3.55 and 3.25 eV for the binary and the ternary alloy, respectively, independent of the anodizing electrolyte. Films grown on the binary alloy present insulating behaviour and anodic impedance spectra with one time constant; this was interpreted in terms of a single-layer mixed Ti–Zr oxide enriched in Ti with respect to the alloy composition. Also for the ternary alloy the results are consistent with the formation, upon anodization, of Ti–Nb–Zr mixed oxide films, but they display n-type semiconducting behaviour, owing to their poor content of ZrO 2 groups.

This work is aimed at studying the growing process of nanostructures electrodeposited from molybdate aqueous solutions at different pH values into pores of polycarbonate membrane templates. The challenging issue was the opportunity to investigate a rather complex deposition process in a confined ambient, where electrochemical conditions are quite different from those usually established for deposition on a flat substrate. Nanostructures were grown from a bath containing Mo7O246– (NH4)6Mo7O24·4H2O) at different concentrations (50–100 g/L), at a constant cathodic current density of 2 mA/cm2 (electrodeposition area ∼8 cm2). Nanostructured deposit was characterized by XRD, EDS, Raman, XPS, and photoelectrochemical spectroscopy. Several parameters have been investigated, such as electrodeposition time, concentration of Mo precursor, and pH. These parameters do not influence the nature of deposit that always consists of mixed valence molybdenum oxides, whereas the nanostructure morphology changes with pH. Nanos...

In this work, we report some preliminary results concerning the fabrication of quaternary semiconductor Cu2ZnSnS4 (CZTS) thin films on a flexible substrate through the simultaneous electrodeposition of elements having different standard electrochemical potentials. CZTS thin films were obtained by potentiostatic deposition from aqueous baths at room temperature and under N2 atmosphere, varying bath composition. Chemical composition and structure of the electrodeposited films were evaluated by EDS, SEM, RAMAN and XRD. Preliminary results on the photoelectrochemical behaviour of the films will be also presented.

Metallic lead was deposited, both in form of bulk films and nanowire array within pores of anodic alumina membranes, following a new two-step procedure, consisting in anodic electrodeposition of α-PbO2, followed by its reduction to metallic lead. This method allows to overcome drawbacks of the “direct” electrodeposition of lead from aqueous solution, consisting, essentially, in the formation of dendritic deposits. Here, we report the comparison between results obtained in the two cases and discuss the kinetic of oxide reduction both for films and nanowires. Deposit morphology and structure are also discussed. We have found that reduction of α-PbO2 films proceeds always at high speed and unitary efficiency, with the formation of polycrystalline compact films. Unfortunately, these films present cracks due to the volume shrinkage accompanying the conversion of α-PbO2 into Pb metal. In addition, α-PbO2 nanowires reduction proceeds up to a complete conversion to metallic Pb, which present a characteristic “sausage-like” shape caused by the lower molar volume of metal with respect to oxide.

The preparation of Sn 2 Co 3 nanowire arrays (NWs) electrogrown inside the channels of polycarbonate membranes and their characterization as anodes for Li-ion batteries both in half-cell vs. Li and in battery configuration are reported. The Sn 2 Co 3 NW electrodes tested by deep galvanostatic charge/discharge cycles in ethylene carbonate-dimethylcarbonate (1:1) – LiPF 6 1 M displayed 80% capacity retention after 200 cycles at C/2 and 30 °C, and a high charge and discharge rate capability at C-rate from C/3 (0.33 A/g) to 10C (10 A/g) at 30° and 10 °C. Electrodes with the highest alloy loading delivered up to 0.6 mAh cm −2 at C/2. The performance of these electrodes in battery configuration with LiFePO 4 as cathode is also reported, as well as the effect of the vinylene carbonate additive on the charge/discharge coulombic efficiency of the Sn 2 Co 3 NWs.

Amorphous SnCo alloy nanowires (NWs) grown inside the channels of polycarbonate membranes by potentiostatic codeposition of the two metals (SnCo- PM ) were tested vs. Li by repeated galvanostatic cycles in ethylene carbonate-dimethylcarbonate – LiPF 6 for use as negative electrode in lithium ion batteries. These SnCo electrodes delivered an almost constant capacity value, near to the theoretical for an atomic ratio Li/Sn of 4.4 over more than 35 lithiation–delithiation cycles at 1 C. SEM images of fresh and cycled electrodes showed that nanowires remain partially intact after repeated lithiation–delithiation cycles; indeed, several wires expanded and became porous. Results of amorphous SnCo nanowires grown inside anodic alumina membranes (SnCo- AM ) are also reported. The comparison of the two types of NW electrodes demonstrates that the morphology of the SnCo- PM is more suitable than that of the SnCo- AM for electrode stability over cycling. Optimization of NW technology should thus be a promising route to enhancing the mechanical strength and durability of tin-based electrodes.

Metallic lead nanowires were deposited within pores of commercial anodic alumina membranes having an average pore diameter of 210 nm. "Direct" electrodeposition was attempted from 0.1 M Pb(NO 3 ) 2 aqueous solution with a variable concentration of H 3 BO 3 as a chelating agent, but it gave unsatisfactory results. An "indirect" two-step deposition procedure was then adopted, consisting of the anodic electrodeposition of α-PbO 2 nanowires, followed by their in situ reduction to metallic lead. Both these processes occurred at a high rate so that the indirect method led to a complete template pore filling with pure polycrystalline Pb in short times and with a high current efficiency.

Ordered arrays of α-PbO 2 nanostructures were grown by galvanostatic anodic deposition into the channels of alumina templates. Electrodepositions were performed in an aqueous solution containing lead acetate and sodium acetate at pH 5.4. Bath temperature and electrodeposition time were varied to check their effect on the growth of nanostructures. It has been found that filling of alumina pores is independent of the time and electrodeposition temperature, whilst height and growth kinetics of nanostructures vary with both parameters. Temperature greatly influences morphology: wires grown at room temperature consisted of clusters of particles, leading to poorly compact structures, whilst at 40 °C the formation of compact wires was observed, some of them being partially hollow. Finally, nanowires with a very regular and dense structure were obtained at 60 °C. Also crystalline structure changes with temperature: polycrystalline nanostructures, with a preferential orientation and an average grain size of 21 nm, were obtained at room temperature, whilst at higher temperatures, wires grew almost exclusively along the plane (2 0 0) with an average grain size of approximately 28 nm. Real surface area of nanowires was evaluated from the FEG-SEM images, and it was found two orders of magnitude greater than the geometrical one.

The present paper focuses on a nanostructured SnCo alloy electrochemically prepared by template method in view of its use as anode material alternative to graphite in lithium-ion batteries. The fabrication of SnCo nanowire arrays was carried out by potentiostatic co-deposition of the two metals by using nanostructured anodic alumina membranes as template. Electrochemical tests on lithiation-delithiation of these SnCo electrodes in conventional organic electrolyte (EC:DMC LiPF6) at 30°C showed that their specific capacity was stable for about the first 12 cycles at a value near to the theoretical one for Li22Sn5 and, hence, progressively decayed.

A suitable hydrometallurgical and environmentally friendly process was studied to replace the currently used practices for recycling lead-acid batteries via smelting. Metallic lead was recovered by cementation from industrial lead sludge solutions of urea acetate (200 to 500 g/L) using different types of metallic iron substrates (nails, shaving or powder) as reducing agents. Under specific operating conditions, up to 99.7% of lead acid battery paste, mainly composed of PbSO4, PbO2 and PbO·PbSO4 species, was converted to metallic lead.. The conversion of the metallic lead and rate of the cementation reaction were strictly dependent on the type of iron substrate used as the reductant and the best operating conditions were found with iron powder. The rate constant of the lead recovery reaction under these conditions was 3 · 10− 3 1/s and the rate determining process was the diffusion controlled cathodic reaction (Ea = 1.9 kJ/mol). The reaction residues and the recovered lead were characterized by XRD analysis. Metallic lead morphology and purity were studied by SEM and EDS respectively. Addition of proper amounts of concentrated sulphuric acid to the exhausted cementation solution led to the quantitative recovery of iron(II) by crystallization of (NH4)2SO4FeSO4.6H2O.

Nanowires of Sn-Co alloys were grown inside the channels of anodic alumina membrane by potentiostatic deposition. The scanning electron microscope images showed the formation of cylindrical nanowires whose height was increasing with deposition time. The X-ray patterns did not show significant diffraction peaks, suggesting the formation of amorphous phases. The higher content of Co in the nanowires, in comparison to the initial composition of the electrolytic bath, was attributed to a higher rate of Co electrodeposition. These nanowires seem to possess specific features suitable for innovative application in the field of Li-ion batteries due to their dimensional stability and high specific surface.

Metallic copper nanowires have been grown into the pores of alumina membranes by electrodeposition from an aqueous solution containing CuSO 4 . and H 3 BO 3 at pH 3. In order to study the influence of the electrical parameters on growth and structure of nanowires, different deposition potentials (both in the region where hydrogen evolution reaction is allowed or not) and voltage perturbation modes (constant potential or unipolar pulsed depositions) were applied. In all cases, pure polycrystalline Cu nanowires were fabricated into template pores, having lengths increasing with the total deposition time. These nanowires were self-standing, because they retain their vertical orientation and parallel geometry even after total template dissolution. However, the electrical parameters influence the growth rate, length uniformity and crystal size of the nanowires. Continuous electrodeposition resulted in higher growth rates but less uniform lengths of nanowires grown inside different membrane pores, whilst a square pulse deposition produced a slower growth but quite uniform lengths. Also the grain size, of the order of 50 nm, was slightly influenced by the potential perturbation mode.

Nanotube arrays of CeO2 were produced in a single step by potentiostatic electrochemical deposition from a non-aqueous electrolyte, using anodic alumina membrane templates. The CeO2 nanotubes showed a polycrystalline structure, and they were assembled in the membrane nanochannels. The nanotubes had somewhat uniform diameters, with an average external value of about 210 nm, and a maximum length of about 60 µm; the latter parameter was controlled by the electrodeposition time. Each single nanotube was found to consist of crystalline grains having a size of about 3 nm. Raman analysis shows that these CeO2 nanotubes are suitable for catalytic applications.

Perfectly aligned nanowire arrays of polycrystalline Cu2O were grown by template-pulsed electrodeposition from a cupric acetate-sodium acetate bath into anodic alumina membranes (AAM). The photoelectrochemical behavior of arrays with different nanowire lengths (0.5 mu m and 2 mu m) was investigated in neutral solution, and the results compared to those pertaining to Cu2O films grown with the same procedure. Although all samples displayed the same indirect bandgap (similar to 1.9 eV), differences were observed both in photocurrent intensity and sign. The latter changed with potential and wavelength in different ways for nanowires and films, revealing a different defect concentration in the two cases.

In recent years, the increased demand for hydrogen in many industrial applications, like petrochemical and semiconductor processing, and sustainable energy (fuel cells) has led to a renewed interest in methods for separation and purification of hydrogen from gas mixtures. In particular, palladium-based membranes have been the subject of many studies, due to their potential use as hydrogen-selective membranes for gas separation or purification [1,2]. Owing to the high cost of palladium and in order to increase the flow rate of hydrogen, composite membranes, formed by a thin layer of palladium deposited on a porous support, are largely preferred to thick self-standing metal membranes. Different supports were extensively used to prepare composite membranes resistant to the high temperature required for fast gas permeation through a dense palladium layer. A severe drawback in using composite membranes is due to the possible presence in the palladium layer of pinholes and/or cracks, which reduce the selectivity.

The fabrication of alumina membranes by electrochemical oxidation of annealed aluminium was investigated. Porous layers were grown in 0.4 M H3PO4 at −1 and 5 °C at different anodising times. The morphology of the outer surface was found to be dependent on temperature and charge density, with both determining the extent of chemical dissolution of the anodic oxide. The inner-surface morphology was found to depend on the applied voltage only. The chemical dissolution rate of anodic oxide grown on annealed aluminium was found to be lower than that formed on unannealed aluminium under otherwise identical conditions. Such a difference in behaviour is explained in terms of a higher finishing degree of annealed aluminium determining a lower defect concentration in the anodic oxide.