One-pot synthesis of Bi-Ni nanowire and nanocable arrays by coelectrodeposition approach
© Jia et al; licensee Springer. 2012
Received: 26 September 2011
Accepted: 15 February 2012
Published: 15 February 2012
A novel and convenient one-pot electrodeposition approach has been developed for precisely controlled fabrication of large-scale Bi-Ni nanowire and nanocable arrays. Using porous anodic aluminum oxide as a shape-directing template, by simply changing the electrochemical deposition mode, desired Bi-Ni hybrid nanowires and Bi-Ni core-shell nanocables have been obtained in the CV and CC modes, respectively. The structure, morphology, and composition of the as-prepared samples were characterized using X-ray powder diffraction, transmission electron microscopy, elemental mapping, and energy-dispersive X-ray spectrometry.
KeywordsBi-Ni nanocables Bi-Ni nanowires AAO coelectrodeposition
One-dimensional hetero-nanostructures, such as nanocables [1–3], nanowires [4–6], superlattice nanowires [7–9], and nanobelts [10–13], have attracted great interest in recent years. Among various fabrication strategies, electrochemical template deposition is a simple and versatile method because the well-defined templates allow us to control the length, diameter, and component of one-dimensional [1D] nanostructures. Recently, Xue et al.  developed a pulsed electrodeposition technique for the synthesis of Bi/Sb superlattice nanowire arrays with longitudinally ordered heterostructures. They synthesized four kinds of a modulated structure of Bi/Sb superlattice nanocables with different periods. Almost at the same time, Wang et al.  demonstrated the synthesis of Cu/Ni nanocables by codepositing nickel and copper atoms into the pores of anodic alumina membranes. Other heterostructures, such as Pd/Fe , Pd/Ni , ZnO/Cu2O , CdS/SnS , and CdS/TiO2 , have also been prepared by electrodeposition. However, since a depositing metal is different from a depositing semiconductor, it is still a critical challenge to controllably produce metal/semiconductor nanostructures with a designed morphology in one-step electrodeposition.
Bismuth (Bi) is a semimetal with unusual electronic properties that result from its highly anisotropic Fermi surface, low carrier concentration, small effective mass, and long mean free path of the carriers . Because of these unique features, Bi has been extensively investigated for quantum transport, finite-size effects, and giant magnetoresistance effects . Furthermore, Lee et al.  observed a semimetal-to-semiconductor transition when the diameter of Bi nanowire was smaller than 63 nm. The Bi-Ni heterojunction formation is therefore highly attractive not only for the incorporation of a magnetic property , but also for the introduction of semimetal and semiconductive behaviors into the structures. However, due to the relatively low conductivity of semimetal and semiconductive species, the one-step preparation of a metal/semiconductor heterojunction is challenging, particularly for the controllable formation of 1D nanocables. In this paper, we report a facile one-pot electrodeposition and anodic aluminum oxide [AAO] template-assisted method for growing uniform and well-aligned 1D Bi-Ni heterojunctions at a low temperature. 1D Bi-Ni hybrid nanowires and Bi-Ni core-shell nanocables have been successfully fabricated in a controlled fashion just by simply changing the electrodeposition conditions.
Fabrication process of the AAO template
All reagent are of analytical grade and used without further purification. AAO template was prepared by a two-step anodization method. A high-purity Al foil (99.999%, Beijing Mengtai Technology Development Co., Ltd., Beijing, China) was first annealed at 500°C for 4 h under nitrogen atmosphere followed by electropolishing with a voltage of 5 V in a mixture of HClO4 and C2H5OH (1:3 v/v). The electropolished Al foils were subjected to the first-step anodization for 4 h in a solution of 0.3 M oxalic acid (40 V, 0°C, graphite as a cathode). The first-step anodized layer was removed by etching in a mixture of phosphoric acid and chromic acid at 60°C for 8 to 10 h. The samples were thoroughly rinsed in distilled water and anodized again in 0.3 M oxalic acid (40 V, 0°C, graphite as a cathode). After the second-step anodization, the unwanted aluminum matrix was dissolved in a saturated CuCl2 solution at room temperature. Finally, the template was rinsed with distilled water and immersed in 5% phosphoric acid for about 20 to 40 min at 65°C to adjust the pore diameter and remove the barrier layer at the bottom of nanoholes.
One-step synthesis of Bi-Ni nanowire and nanocable arrays
The morphology of the oriented Bi-Ni nanowire and nanocable arrays was characterized using an S-4800 field-emission scanning electron microscope [FE-SEM] (Hitachi, Chiyoda-ku, Tokyo, Japan). Prior to SEM observation, several drops of a 1-M NaOH aqueous solution were added onto the sample to dissolve the AAO template. The residual solution on the surface of the template was rinsed with distilled water. The structure of the resulting material was characterized by X-ray diffraction [XRD] (Rigaku, Shibuya-ku, Tokyo, Japan) with Cu Kα radiation at room temperature. Further detailed structural information of the oriented Bi-Ni nanowire and nanocable arrays was obtained using a Tecnai G2 F20 U-TWIN field-emission transmission electron microscope [TEM] (FEI, Shanghai, China) equipped with an energy-dispersive X-ray spectroscopy [EDS] system, digital scanning attachment, and high-angle annular dark field [HAADF] detector. In this paper, we have focused on the structural and compositional analyses of the nanowire and nanocable distribution using a combination of EDS in a scanning electron transmission microscopy [STEM] mode. For TEM observation, the template was completely dissolved in a 2-M NaOH aqueous solution. The product was centrifuged, thoroughly washed with distilled water to remove residual NaOH, and then dispersed in alcohol with the aid of ultrasonic agitation for 30 min. After that, a drop of solution was dropped onto a copper grid covered by porous carbon.
Results and discussion
Figure 4b depicts the STEM images and elemental maps of the Bi-Ni nanocable specimen. As can be seen, nickel distribution is very uniform over the entire cable area (Figure 4biii); in contrast, bismuth tends to populate in the center of the cables (Figure 4biv). Figure 4bi gives the corresponding STEM HAADF image of the nanocable. Again, a minor amount of beam damage (Figure 4bii) and a sample drifting phenomenon were detected after the EDS scanning of these HAADF images.
In summary, a novel and convenient one-pot electrodeposition approach has been developed for precisely controlled fabrication of large-scale Bi-Ni hybrid nanowire and Bi-Ni core-shell nanocable arrays. During the reaction process, AAO is used as a shape-directing template. By simply changing the electrochemical deposition mode, desired Bi-Ni hybrid nanowires and Bi-Ni core-shell nanocables have been obtained in the CV and CC modes, respectively. The present synthesis strategy may be extended to controllable fabrication of other 1D metal/semiconductor heterojunctions and their arrays.
anodic aluminum oxide
energy-dispersive X-ray spectroscopy
field-emission scanning electron microscope
high-angle annular dark field
scanning electron transmission microscopy
transmission electron microscope
This work was supported by the National Natural Science Foundation of China (grant no. 20973044), the Ministry of Science and Technology of China (no. 2009AA03Z328 and no. 2009DPA41220), and the Chinese Academy of Sciences (no. KJCX2-YW-H21).
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