Tube Formation in Nanoscale Materials
© to the authors 2008
Received: 10 October 2008
Accepted: 17 October 2008
Published: 4 November 2008
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© to the authors 2008
Received: 10 October 2008
Accepted: 17 October 2008
Published: 4 November 2008
The formation of tubular nanostructures normally requires layered, anisotropic, or pseudo-layered crystal structures, while inorganic compounds typically do not possess such structures, inorganic nanotubes thus have been a hot topic in the past decade. In this article, we review recent research activities on nanotubes fabrication and focus on three novel synthetic strategies for generating nanotubes from inorganic materials that do not have a layered structure. Specifically, thermal oxidation method based on gas–solid reaction to porous CuO nanotubes has been successfully established, semiconductor ZnS and Nb2O5nanotubes have been prepared by employing sacrificial template strategy based on liquid–solid reaction, and an in situ template method has been developed for the preparation of ZnO taper tubes through a chemical etching reaction. We have described the nanotube formation processes and illustrated the detailed key factors during their growth. The proposed mechanisms are presented for nanotube fabrication and the important pioneering studies are discussed on the rational design and fabrication of functional materials with tubular structures. It is the intention of this contribution to provide a brief account of these research activities.
Recently, considerable attention has been focused on micro- and nanostructured materials due to their unique properties and potential applications in many aspects [1–5], among which nanotubes have been attracting special interests since Iijima’s identification of carbon nanotubes . The tubular form is particularly attractive because it provides access to three different contact regions, inner and outer surfaces as well as both ends. However, for a long time the nanotube formation is generally limited to layered materials, through the bending of thin crystal flakes. Due to the weakness of interlayer interactions (van der Waals forces) and to the dangling bonds that can be eliminated by interlayer covalent bonds, nanotubes formation is very analogous to the case of carbon nanotubes based on a “rolling-up” mechanism . A number of studies have been devoted to generating nanotubes from most kinds of materials [6–8], which clearly indicate that solid materials can be prepared as nanotubes by properly selecting proper preparation methods, for example, BN, V2O5, NiCl2, TiO2, and other materials with tubular structures [9–14].
Inorganic tubular structures become a symbol of the new and fast-developing research area due to their tremendous applications for over a decade. Inorganic nanotubes are less well studied, in part due to difficulties in well controlling their dimensions . However, inorganic nanotubes still share many advantages of carbon nanotubes and can match increasing demand for various functions. Non-carbon materials , for example, titania nanotubes have been studied and show improved properties compared to colloidal or other forms of titania for applications in photocatalysis [17, 18], sensing , and photovoltaics [20, 21].
The past couple of decades have witnessed an exponential growth of activities in the synthesis of nanotubes, driven by both excitement of understanding new science and the potential hope for applications and economic impacts. The numerous potential applications of inorganic nanotubes have been highlighted in a number of recent studies [17–21]. The present article reviews the classical methods and some recent contributions to the synthesis of nanotubes from inorganic materials that do not contain layered structure. We explicitly describe three different approaches for fabrication of tubular nanostructures, each approach is highlighted by at least one example.
Similarly to the gas-action route, there have been significant research efforts devoted to nanotubes of layered or anisotropic crystal structured materials in solution, including WO3 · H2O , Cu(OH)2, SrAl2O4, CeO2, and CeO2−x . The bending and roll-up of a thin layer to form tube is a thermally driven process. From a kinetic viewpoint, the rolling of layered structure may be initiated by a stress of either a structure or an electrical nature caused by the asymmetry of the layer. Though many nanotubes of layered or artificial lamellar structures have been successfully achieved, this strategy cannot be applied to non-layered materials.
Although the template-based methods are regarded as a simple and very effective way for preparing nanotubes, this route requires the use of a base or acid medium or high temperature to remove templates, which increases the cost and risk of large-scale manufacture. Recently, a new synthetic strategy is promoted, whereby nanorod or nanowire precursors are first generated in situ and act as the self-sacrificing template for growing nanotubes. The template can act not only as simply inert shape-defining molds but also as chemical reagents for the creation of nanotubes. For example, ultra-long single-crystal ZnAl2O4 spinel nanotubes were fabricated through a spinel-forming interfacial solid-state reaction of core-shell ZnO–Al2O3 nanowires involving the Kirkendall effect . Single-crystal Cd3P2 and Zn3P2 nanotubes were synthesized by this chemical strategy . This process involves the in situ formation of Zn and Cd metal cores, Cd3P2 and Zn3P2 shells, and finally the semiconductor nanotubes.
Uniform goethite nanotubes with a parallelogram-shaped cross section have been fabricated via this synthetic procedure . Hydrazine was added and induced the reaction with the Fe3+–oleate complex. Subsequent crystallization resulted in the formation of 2 nm-sized spherical nanoparticles of iron oxide or related iron-containing compounds. Further aging induced the directional assembly of the 2 nm-sized nanoparticles onto the reverse micelle template, generating the nanotubes.
As a well-known transition metal oxide, copper oxide (CuO) has been extensively studied because of its applications in the field of lithium-ion batteries, catalysis, and superconductors . We have proposed a general thermal oxidation method to synthesize porous CuO nanotubes based on a gas–solid reaction between CuSe nanowires and O2. The current strategy is based on the combination of Kirkendall effect, volume loss, and gas release. Porous CuO nanotubes are used as example to demonstrate this general top–down chemical approach.
The oxidation rate has an important effect on the morphology of final products. When the oxidation was carried out in a furnace at a previously maintained temperature of 700 °C, the non-equilibrium interdiffusion, volume loss, and gas release strongly accelerated, and the tubular structure then collapsed. The obtained CuO nanotubes with a porous shell might be more attractive than closed hollow structures in some aspects such as catalysis, because of the dense distribution of pores in their walls. More importantly, our thermal oxidation method is quite versatile and can be extended to other transition metal chalcogenides.
As a very important direct wide-band-gap semiconductor with the highest band gap of 3.6 eV among all II–VI compounds, ZnS has received much attention due to its excellent properties and is extensively used as displays, sensors, and lasers [42, 43]. Recently, nanoscale metal sulfides are assuming great importance in both theory and practice, owning to their novel properties as a consequence of a large number of surface atoms and the three-dimensional confinement of electrons . These unique properties lead to appearance of many new application areas such as solar cells, photodetectors, light-emitting diodes, and laser communication.
An evolution in particle shape from ZnO nanorod to ZnS nanotube array is due to the solubility difference between ZnO and ZnS and to the assistance of thioglycolic acid. ZnO nanorod arrays were used as a template for the fabrication of ZnO/ZnS nanocables by sulfurization of ZnO after a thioglycolic acid-assisted reaction. When ZnO nanorod arrays were introduced into HSCH2COOH solution, ZnHS+complex could be formed between the lone pair electrons of sulfur atom of HSCH2COOH molecule and the vacantd orbital of the Zn2+ions, which results in an increase in the activity of Zn2+ions on ZnO nanorods, and then ZnS nucleates and grows by dissolution of ZnO nanorods. After reaction, ZnO/ZnS nanocables can be obtained. Since ZnO has an amphoteric characteristic, KOH treatment of ZnO/ZnS nanocables leads to the dissolution of ZnO cores, and thus ZnS nanotube arrays can be successfully obtained. The well-aligned ZnS nanotube arrays were observed on the surface of zinc foil, as shown in Fig. 6d. It can be seen that ZnS tubes have open ends with a uniform pore size.
Oxide nanotubes of several transition metals and other metals have been synthesized employing different methodologies. As one of the group V–B oxides, niobium oxide (Nb2O5) is an important n-type semiconductor with a wide band gap of about 3.4 eV, and has found important applications in solar cells, sensors, advanced catalysts, and electrochromic devices .
It is a novel sacrificial template route to prepare Nb2O5nanotube by employing pseudo hexagonal Nb2O5as template to monoclinic products. Monoclinic Nb2O5with tunable diameter was fabricated through a phase transformation process between pseudo hexagonal and monoclinic Nb2O5nanotube, which involves a non-equilibrium interdiffusion process accompanied by the void generation in solution reaction system. A key parameter for achieving nanotube growth is the energy difference between the pseudo hexagonal and monoclinic Nb2O5nanostructures, which determines the phase transformation.
Currently, the template-directed synthesis of functional materials is arousing increasing interest due to its unique advantages in the control over shape, size, and crystal growth [2, 43, 46]. It represents a straightforward and efficient route towards hollow structures. However, these reported template strategies often suffer from the great difficulty to separate hollow structures from template, which is still a big challenge for the synthesis of hollow structures. We believe that direct methods in which synthesis and template elimination are coupled in situ to produce hollow structures have great applications, due to the fact that the difficulty of removing template from the reaction system can be effectively avoided. ZnO, a well-known direct-bandgap semiconductor, represents one of the most important materials of the wurtzite family, with many remarkable applications in electronics, photoelectronics, and sensors [47–49].
The hexagonal wurtzite structure ZnO can be simply described as a number of alternating planes composed of tetrahedrally coordinated O2− and Zn2+ ions, stacked alternately along the c-axis. Considering the atom arrangement forms of the specific planes, the (001) face of ZnO crystal contains Zn atom only, whereas (00-1) face consists of oxygen atom. The positively charged ZnO (001)-Zn surface is chemically active, and the negatively charged (00-1)-O surface is inert. Therefore, the selectively etching ZnO taper appears to take place preferentially at the (001) face, which is a typical phenomenon for wurtzite-structured materials well interpreted by chemical bonding theory . Herein, we have developed an in situ template strategy for the synthesis of ZnO tubes through chemical etching reaction, which avoids the multiple steps that are currently used in the preparation of other hollow materials . The chemical etching in situ formed ZnO template is related to its intrinsic symmetry of the corresponding lattice and chemical activities.
The inorganic nanotubes possess several characteristics that are beneficial for their applications in optoelectronics and catalysis. In particular, the ability to synthesize and control the inner diameter of nanotubes makes the nanotube-based device/system a unique tool for further applications. This article summarizes recent progresses on the synthesis of inorganic nanotubes. New synthetic strategies for the tube formation in nanoscale have been developed. Three different approaches to the production of high-quality semiconductor nanotubes have been demonstrated. A thermal oxidation route by employing gas–solid reaction to porous CuO nanotubes, a sacrificial template strategy for the synthesis of ZnS and Nb2O5nanotubes based on liquid–solid reaction, and an in situ template route to ZnO taper tubes through a chemical etching reaction have been successfully developed. Combined together, these approaches have greatly expanded the scope of inorganic materials that can be processed as nanotubes with uniform and controllable dimensions. We believe that these techniques can be readily extended to produce more complex nanostructures with hollow interiors and cover a broader range of materials than those presented in this article by incorporating more reactions and thus more solid materials into the synthetic process. The scientific and technical potential of these novel nanotube structures are certainly bright and there are great research opportunities that will be explored by many chemists, physicists, and material scientists around this general area.
The authors gratefully acknowledge the financial support of NCET-05-0278, NSFC #20471012, and FANEDD #200322.