低速电沉积钯镍合金工艺的研究

通过极化曲线研究了钯、镍的电沉积行为.讨论了钯镍浓度比、pH值、电流密度、沉积电势等工艺参数对低速电沉积钯镍合金组成的影响.结果表明:与钯相比,镍的极化大,极化度也大;电沉积合金时,钯催化镍的沉积,而镍阻化钯的沉积.合金组成是各工艺参数的函数,镀液中钯、镍离子浓度比是影响合金成分的主要因素.随着镀液中Ni/Pd值的增大,合金中镍含量呈线性增加;pH值升高,合金中镍含量降低;电流密度增大或者沉积电势负移,合金中镍含量增加;沉积电势对合金成分的影响更显著,成分更易控制.     

Electrochemically stable gold nanoclusters in HOPG nanopits

Gold nanoparticles on highly oriented pyrolytic graphite (HOPG) electrodes are synthesized. They are stabilized in nanosized pits of well defined depth in the graphite surface. These pits are created by energetic cluster impact followed by etching under a well controlled oxygen atmosphere. We succeeded in the preparation of highly dispersed and stable Au electrodes with gold particles with a mean diameter smaller than 5 nm. The stability of the gold nanostructures for electrochemical applications has been tested by performing cyclic voltammetric measurements in 0.5 M H₂SO₄. While conventionally prepared sputter deposited electrodes show highly unstable structures in this size range, Au clusters stabilized in the nanosized containers are stable.     

Enhancement of adsorption on graphite (HOPG) by modification of surface chemical functionality and morphology

The effects of chemical functional groups and surface morphology on the adsorption/desorption behavior of a model non-polar organic adsorbate (propane) on model carbonaceous surfaces [air-cleaved highly oriented pyrolytic graphite (HOPG) and plasma-oxidized HOPG], were investigated using temperature-programmed desorption (TPD). Oxygen- and hydrogen-containing functional groups exist on both air-cleaved HOPG and plasma-oxidized HOPG. The presence of these groups almost completely suppresses propane adsorption at 90 K. However, these groups can be removed from both air-cleaved and plasma-oxidized HOPG by thermal treatment (>500 K), leading to more than an order of magnitude increase in adsorption capacity. It is essential for both air-cleaved HOPG and plasma-oxidized HOPG to be outgassed at over 1273 K for all the adsorption sites to be chemically accessible for propane molecules. The effect of morphological heterogeneity is evident for plasma-oxidized HOPG as this substrate provides greater surface area available for adsorption, as well as higher energy binding sites.     

An STM study of phosphoric acid inhibition of the oxidation of HOPG and carbon catalyzed by alkali salts

The role of phosphoric acid as an inhibitor in the oxidation of HOPG and as a neutralizer of alkali salt catalysts is examined using scanning tunneling microscopy, supported by thermogravimetric analysis of carbon powder samples. HOPG samples were oxidized in air primarily at 700 °C, with a few samples oxidized at 800 °C. Reaction time was 20 min. Powder samples were oxidized for 5 min at temperatures ranging from 500 °C to 900 °C and rates of oxidation were determined. STM images of impurity deposits and oxidized samples are presented and analyzed. Two alkali salts are examined, sodium hydroxide and potassium acetate, and both catalyze oxidation at 700 °C. Phosphoric acid proves to be an inhibitor at 700 °C but begins to lose its inhibiting effect at 800 °C. It also demonstrates neutralization of potassium acetate at 700 °C but results for NaOH/phosphoric acid mixtures are less conclusive.     

Fabrication of vertically aligned Pd nanowire array in AAO template by electrodeposition using neutral electrolyte

A vertically aligned Pd nanowire array was successfully fabricated on an Au/Ti substrate using an anodic aluminum oxide (AAO) template by a direct voltage electrodeposition method at room temperature using diluted neutral electrolyte. The fabrication of Pd nanowires was controlled by analyzing the current–time transient during electrodeposition using potentiostat. The AAO template and the Pd nanowires were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) methods and X-Ray diffraction (XRD). It was observed that the Pd nanowire array was standing freely on an Au-coated Ti substrate after removing the AAO template in a relatively large area of about 5 cm², approximately 50 nm in diameter and 2.5 μm in length with a high aspect ratio. The nucleation rate and the number of atoms in the critical nucleus were determined from the analysis of current transients. Pd nuclei density was calculated as 3.55 × 10⁸ cm⁻². Usage of diluted neutral electrolyte enables slower growing of Pd nanowires owing to increase in the electrodeposition potential and thus obtained Pd nanowires have higher crystallinity with lower dislocations. In fact, this high crystallinity of Pd nanowires provides them positive effect for sensor performances especially.     

Control of composition and size for Pd–Ni alloy nanowires electrodeposited on highly oriented pyrolytic graphite

In order to fabricate effective Pd–Ni alloy nanowire arrays with given compositions and size, the process of nucleation and growth and the dependence of alloy composition on deposition potential were investigated. The results reveal that the compositions and sizes of Pd–Ni alloy nanowires can be controlled within a desired range through adjusting suitable nucleation and growth potentials as well as the time. The Ni content in the alloy nanowires was found to vary from 6 to 28% when the deposition potential was changed from −0.3 to −1.9 V. A growth potential of −0.35 to − 0.50 V was applied to fabricate Pd–Ni alloy nanowires with 8–15% Ni content. Continuous and parallel nanowire arrays can be successfully fabricated when nucleation is performed at a potential of −1.2 V for 50 ms with further growth at −0.45 V for 800 s. Pd–Ni crystal phases exist in the alloy structure forms of 〈111〉, 〈200〉, 〈220〉, 〈311〉. The nanowires have an average diameter of 150 nm and a length of 100–450 μm.     

Tuning the architectures of lead deposits on metal substrates by electrodeposition

Different morphologies of lead (Pb) deposited on different metal substrates have been prepared via electrochemical deposition in aqueous solution. The morphologies of as-deposited lead were determined by scanning electron microscope (SEM). It is found that the various morphologies of the products are dependent on the electrodeposition conditions, including the deposition current densities, concentration of additives, substrates and deposition time. X-ray diffraction (XRD) and transmission electron microscope (TEM) results reveal that all these lead deposits with different morphologies can be assigned to the space group Fm-3m (2 2 5).     

Fabrication of integrated arrays of ultrahigh density magnetic nanowires on glass by anodization and electrodeposition

Integrated nanowire arrays of Fe-Pt, Co-Pt, and Ni-Pt alloys were successfully fabricated on glass substrates by successive anodization and electrodeposition. Porous alumina films, which were formed from an aluminum layers sputter-deposited on glass substrates covered with transparent oxide conductive films, were used as template-electrodes to deposit various magnetic alloys (Fe-Pt, Co-Pt, and Ni-Pt) in the nanopores by a cathodic electrodeposition, thus leading to integrated nanowire arrays with ultrahigh densities of (0.6-2.1) × 10¹⁵ wire m⁻². The as-deposited nanowires of Fe-Pt, Co-Pt, and Ni-Pt alloys are polycrystalline and composed of fine crystals (4-7 nm across) of chemically ordered tetragonal FePt, CoPt, or NiPt phase. The integrated nanowire arrays may be the promising candidate materials for ultrahigh density perpendicular magnetic recording media in terabits per square inch regime, due to the predictable enhanced perpendicular magnetic performance after appropriate annealing.     

Electrochemical preparation and surface properties of gold nanowire arrays formed by the template technique

A new procedure for preparing free-standing nanowire arrays is described. This is based on a template method which entails electrochemical metal deposition into nanometer-wide parallel pores of porous anodic oxide films on aluminum. By varying the preparation conditions and by applying electrochemical posttreatment methods, gold nanowire arrays are prepared, whose morphological and dimensional properties and oxygen content in the nanowire surface can be varied and investigated by SEM and XPS-characterization. The voltammetric behaviour of such nanowire arrays shows a significant enhancement of the ratio between the total electrolytically exposed surface area and the diffusionally accessible surface area in comparison with macroscopic flat gold electrodes.     

Electrocatalysis of oxygen reduction by quinones adsorbed on highly oriented pyrolytic graphite electrodes

The reduction of oxygen in alkaline solution has been studied on highly oriented pyrolytic graphite (HOPG) electrodes modified with various quinones using a rotating disk electrode (RDE). The electrode surface was modified by adsorption of quinones from a 0.1 M KOH solution. The oxygen reduction activity of these electrodes was considerably higher than that for unmodified HOPG and characteristic current maxima for oxygen reduction was observed. All quinones studied catalysed the two-electron reduction of oxygen to hydrogen peroxide. The peak potentials for oxygen reduction were in good correlation with the redox potentials of the quinones that were found from the cyclic voltammograms in oxygen-free solutions. The results obtained give further evidence that oxygen reduction is catalysed by the semiquinone radical and that the redox potential of the quinone is the most important factor determining its electrocatalytic activity for oxygen reduction.     

Fabrication of Ni-silicide/Si heterostructured nanowire arrays by glancing angle deposition and solid state reaction

This work develops a method for growing Ni-silicide/Si heterostructured nanowire arrays by glancing angle Ni deposition and solid state reaction on ordered Si nanowire arrays. Samples of ordered Si nanowire arrays were fabricated by nanosphere lithography and metal-induced catalytic etching. Glancing angle Ni deposition deposited Ni only on the top of Si nanowires. When the annealing temperature was 500°C, a Ni₃Si₂ phase was formed at the apex of the nanowires. The phase of silicide at the Ni-silicide/Si interface depended on the diameter of the Si nanowires, such that epitaxial NiSi₂ with a {111} facet was formed at the Ni-silicide/Si interface in Si nanowires with large diameter, and NiSi was formed in Si nanowires with small diameter. A mechanism that is based on flux divergence and a nucleation-limited reaction is proposed to explain this phenomenon of size-dependent phase formation.     

Electrochemical performance of Sn film reinforced by Cu nanowire

Sn/Cu nanowire composite film was electrodeposited on copper foil substrates and used as an anode material for lithium-ion batteries. The structure of the obtained composite film anode was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical performance was evaluated by cyclic voltammetry, galvanostatic cycling and impedance spectroscopy. It was found that the Sn/Cu nanowire composite film anode showed a better cycle stability than Sn film anode, whereas the Sn/CNT composite film anode indicated poor capacity retention. It could be deduced that copper nanowire reinforced the Sn film anode due to the better wetting property of Sn on the surface of copper and reduced the loss of electric contact among tin particles in the Sn/Cu nanowire composite film anode.     

Fabrication and characterization of hexagonally patterned quasi-1D ZnO nanowire arrays

Quasi-one-dimensional (quasi-1D) ZnO nanowire arrays with hexagonal pattern have been successfully synthesized via the vapor transport process without any metal catalyst. By utilizing polystyrene microsphere self-assembled monolayer, sol–gel-derived ZnO thin films were used as the periodic nucleation sites for the growth of ZnO nanowires. High-quality quasi-1D ZnO nanowires were grown from nucleation sites, and the original hexagonal periodicity is well-preserved. According to the experimental results, the vapor transport solid condensation mechanism was proposed, in which the sol–gel-derived ZnO film acting as a seed layer for nucleation. This simple method provides a favorable way to form quasi-1D ZnO nanostructures applicable to diverse fields such as two-dimensional photonic crystal, nanolaser, sensor arrays, and other optoelectronic devices.     

Electrodeposition of Pd–Ag alloy nanowires on highly oriented pyrolytic graphite

This paper reports findings of an investigation of Pd–Ag alloy nanowires on the step edges of highly oriented pyrolytic graphite (HOPG) by electrochemical deposition at room temperature. Scanning electron microscopy (SEM) images reveal that these alloy nanowires (109–430 nm) are uniform in diameter, and have lengths up to 100–500 μm. The electrodeposition process involves the initial formation of nanowires induced at the step edges of the oxidized HOPG substrate at a very negative potential and subsequent growth at a constant low current density to coalesce the discontinuous nanowires. Alloy nanowires with a 20–25% silver content can be obtained when the ratio of Pd and Ag in the solution is carefully controlled. The SEM images demonstrate that the alloy nanowire arrays are continuous, parallel, ordered, well-aligned and have a narrow distribution of diameters. The Pd–Ag alloy nanowire arrays are promising materials for fabricating hydrogen nanosensors.     

Fabrication of morphology controllable rutile TiO2 nanowire arrays by solvothermal route for dye-sensitized solar cells

Highly ordered, vertically oriented TiO₂ nanowire arrays (TNAs) are synthesized directly on transparent conducting substrate by solvothermal procedure without any template. The X-ray diffraction (XRD) pattern shows that TiO₂ array is in rutile phase growing along the (0 0 2) direction. The field-emission scanning electron microscopy (FE-SEM) images of the samples indicate that the TiO₂ array surface morphology and orientation are highly dependent on the synthesis conditions. In a typical condition of solvothermal at 180 °C for 2 h, the TNAs are composed of nanowires 10 ± 2 nm in width, and several nanowires bunch together to form a larger secondary structure of 60 ± 10 nm wide. Dye-sensitized solar cell (DSSC) assembled with the TNAs grown on the FTO glass as photoanode under illumination of simulated AM 1.5G solar light (100 mW cm⁻²) achieves an overall photoelectric conversion efficiency of 1.64%.     

Copper electrodeposition on pyrolytic graphite electrodes: Effect of the copper salt on the electrodeposition process

The electrodeposition of copper on pyrolytic graphite from CuSO₄ or Cu(NO₃)₂ in a 1.8 M H₂SO₄ aqueous solution was investigated. The Cu deposits were formed potentiostatically and characterized by electrochemical methods, scanning electron microscopy, energy dispersive X-ray and X-ray photoelectron spectroscopy. It was found that the deposition of copper in the presence of CuSO₄ induced the codeposition of sulfate anions. In addition, electrochemical quartz crystal microbalance revealed that the increase of the Cu mass was higher than expected from Faraday's law with the CuSO₄/H₂SO₄ solution. These results confirmed the specific adsorption of anions during the Cu deposition. On the other hand, the use of Cu(NO₃)₂ resulted in a non-contaminated surface with different surface morphologies. The Cu nuclei size, the population density and the surface coverage were monitored as a function of the deposition potential. From the analysis of the chronoamperometric curves, the nucleation kinetics was studied by using various theoretical models. Independently of the Cu source, the nucleation mechanism follows a three-dimensional (3D) process. Copper nucleates according to an instantaneous mode when the deposition potential is more negative than −300 mV versus Ag/AgCl, while the nucleation was interpreted in terms of a progressive mode at −150 mV. The nuclei population densities were also determined by using two common fitting models for 3D nucleation and growth (Scharifker-Mostany and Mirkin-Nilov-Heerman-Tarallo). Their values are reported here as a function of the deposition potential.     

Fe21Ni79合金纳米线阵列的制备与磁性

用交流电化学沉积方法,在多孔铝阳极氧化膜的柱形孔内制备直径约60 nm,长度约为9.7 μm的Fe₂₁Ni₇₉合金纳米线.采用扫描电镜、透射电镜、X射线衍射仪和振动样品磁强计对纳米线的形貌 、结构和磁学性质进行了测试.结果表明,Fe₂₁Ni₇₉纳米线排列有序,长径比可控,合金呈fcc结构.当将其在外磁场下进行垂直磁化时,磁滞回线出现较高的矩形比0.86,矫顽力达1203Oe.且随着退火温度升高,矫顽力迅速增大,500℃时达到最大值1315Oe,之后又随退火温度的升高而下降.矩形比也呈现类似的变化规律.     

Fabrication of nanopatterned metal layers on silicon by nanoindentation/nanoscratching and electrodeposition

The present work illustrates a novel approach for the maskless and resistless fabrication of nanopatterned metal layers on Si substrates, based on the combination of nanomechanical surface modification techniques (such as nanoindentation and nanoscratching) and electrodeposition. Single crystal (1 0 0) n-doped Si substrates were first cleaned from native oxide. Nanoindentation and nanoscratching were then used to locally change the substrate microstructure and create regions with reduced electrical conductivity. The substrates were finally mounted as cathode electrodes in a three-electrode electrochemical cell to potentiostatically deposit a Ni layer. Electrodeposition was prevented in regions with modified microstructure, enabling the formation of a patterned Ni layer. The fabrication of several patterns including continuous Ni lines of 200 nm width and several microns length was obtained.     

Fabrication of egg-shell-roofed macroporous nickel films by a template-mediated electrodeposition process

Through an electrostatics-induced adsorption effect, nickel ions were found to be preferentially adsorbed onto the surface of colloidal particles at template top during the template-mediated electrodeposition process for preparing macroporous structures. This phenomenon results in the preferential reduction and growth of nickel on colloid surface on the template top, instead of filling into the channels among the colloids. After removing the template, an egg-shell-roofed macroporous nickel, consisting of macroporous film covered with monolayer of hollow spheres, can be created.