2 Synthesis and Applications of Titanium Oxide Nanotubes

Tohru Sekino
Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Aoba-ku, Sendai 980-8577, Japan sekino@tagen.tohoku.ac.jp Abstract Titanium oxide nanotube (TiO2 nanotube, TNT) is synthesized by the low-temperature solution chemical method via the self-organization to form unique open-end nanotubular morphology with typically 810 and 57nm in outer and inner diameters, respectively. Because of the mutual and synergy combination of its low-dimensional nanostructure and physical-chemical characteristics of TiO2 semiconductor, properties enhancements and novel functionalization are expected in the TiO2 nanotube. In this chapter, synthesis, nanostructures, formation mechanism, various physicochemical characteristics, and prospects of future application for the TiO2 nanotube are described in detail. In such an oxide material, property control and enhancement is possible by tuning appropriate chemical compositions, crystal structures, and composite structures. Therefore, special emphasis is also placed to introduce modication of the nanotubes by doping and/or nanocompositing to meet the requirements as for the environmental friendly and energy creation systems and various functional devices.

2.1 Introduction
After the discovery of carbon nanotube (CNT) [1], large attention has been paid to this unique low-dimensional nanostructured material because of its attractive various physical and chemical functions which arise from the synergy of low-dimensional nanostructure and anisotropy of carbon network, thus known as graphene structure. Till now, large numbers of not only fundamental studies on the structure, electrical, optical, mechanical, and physicochemical properties but also application-oriented research and development, such as single-electron transistor device, eld emission device, fuel cells, and strengthening llers of composites, have been extensively carried out. Besides CNTs, various inorganic nanotubular materials have been reported in nonoxide compounds, boron nitride (BN) [2] and molybdenum disulde (MoSi2 ) [3]; in oxides such as vanadium oxide (V2 O5 ) [46], aluminum oxide (Al2 O3 ) [6], silicon dioxide (SiO2 ) [6, 7], titanium oxide (TiO2 ) [814]; and also in natural minerals like imogolite [15, 16].
T. Kijima (Ed.): Inorganic and Metallic Nanotubular Materials. Topics in Applied Physics 117, 1732 (2010) c Springer-Verlag Berlin Heidelberg 2010 DOI 10.1007/978-3-642-03622-4 2

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Except natural mineral materials, fabrication of nanotubes is roughly classied into two methods; one is the template or replica method, in which some template materials are used to form tubular structure. Many eorts have been paid to fabricate tubular materials including nanotubes by attempting the template/replica method [4, 5, 8, 1214]. The other one is based on the self-structuralization or self-organization of matter during chemical or physical synthesis/fabrication processes. Synthetic imogolite [16], solgelderived SiO2 nanotube [7], chemically prepared TiO2 nanotube [9, 10], and nanotube/nanohole arrays such as Al2 O3 [17, 18] and TiO2 [11, 19] prepared by electrochemically using anodic oxidation of metal lms are the typical systems fabricated by the self-organizing process. Among them, titanium oxide nanotube (TiO2 nanotube, TNT) is one of the promising nanostructured oxides with tubular structure. TiO2 is well known as a wide gap semiconductor oxide. It is, however, inexpensive, chemically stable, and harmless and has no absorption in the visible light region. Instead, it is UV light responsible; electron and hole pair is generated by the UV irradiation, inducing chemical reactions at the surface. Therefore, the most promising characteristic of TiO2 lies in its photochemical properties such as high photocatalytic activity. Due to this reason, it has been widely studied by many researchers from 1950s to utilize TiO2 as a photocatalyst [2022], an electrode of dye-sensitized solar cell [23], a gas sensor [24], and so on. On the other hand, Kasuga et al. [9, 10] have succeeded in the synthesis of nanotubular TiO2 , which has open-end structure with typically 810 and 57 nm in outer and inner diameters, respectively, using a simple and low temperature solution chemical processing. Various methods such as anodizing of metal substrates [11, 19], replica [8, 12, 13], and template methods [14] have been investigated to prepare tubular TiO2 . However, the synthesis method developed by Kasuga et al. is based on a self-organizing and templateless route that is achieved by low temperature process to form nanometer-sized tubular morphology. Using this so-called Kasuga method, many related investigations have been extensively carried out on structural analysis, process optimization, properties evaluation, and so on [2527]. As mentioned above, not only fundamental interests in the formation mechanism and the unique nanotubular structures but also functions enhancements and novel functionalization are hence expected in the TiO2 nanotube because of the mutual and synergy combination of various factors lying in a nanotubular semiconductor: (1) crystal structure, (2) chemical bonding and (3) physical/chemical properties of the matter, and (4) low-dimensional nanostructures/nanospace/nanosurface and (5) self-organization/ordering of the structure. In this chapter, synthesis processing, nanostructures, various properties and prospects of future application for the TiO2 nanotube fabricated by the low temperature solution chemical route are described in detail. In such an oxide material, property control and enhancement are possible by tuning appropriate chemical compositions and crystal structures. Therefore, special

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emphasis is also placed to introduce modication of the nanotubes by doping and/or nanocompositing in order to meet the requirements as per the environmental friendly and energy creation systems and various functional devices.

2.2 Synthesis and Structure of Titanium Oxide Nanotubes

As mentioned before, fabrication of nanotubular TiO2 is classied into two methods: template/replica route [8, 1214] and direct synthesis (i.e., templateless) route. In the former method, some materials, such as organic, inorganic, and metal nanowires/nanorods/whiskers or nanotube/nanohole arrays such as Al2 O3 prepared by anodic oxidation of Al foil, are used as the templates. TiO2 is hence often synthesized by solgel or precipitation methods in solution, and then the templates are removed afterward. Therefore, the size of obtained materials can be easily controlled by the size of template used. Followed by these processing routes, however, the most as-synthesized nanotubes have an amorphous structure, and then they become nanocrystalline nanotubes after appropriate heat treatment. The latter (direct) synthesis route includes low temperature solution chemical method [9, 10] and electrochemical oxidation route from metal substrate or foil, i.e., anodic oxidation of titanium or titanium alloy [19] that also gives amorphous nanotubes. In the case of solution chemical route, crystalline TiO2 nanotube based on the TiO6 octahedron network can be obtained. In this section processing and structures of the TNT will be given. 2.2.1 Low Temperature Solution Chemical Processing Typical TNT is synthesized by the solution chemical route using highconcentration alkaline solution [9, 10]. Various titanium oxide powders including anatase- or rutile-type titania, their mixture, or titanium alkoxide can be used as the source materials of TNT. The raw material is reuxed in 10 M NaOH aqueous solution at around 110 C for 20 h or longer. The resultant product is washed many times by distilled water in order to remove sodium. Then 0.1 M HCl aqueous solution is added to neutralize the solution and again treated with distilled water until the solution conductivity reached 5 mS/cm. The product is then separated by ltering, centrifugation, or freeze drying technique and dried. This synthesis is carried out under the reuxing condition so that the pressure during synthesis is the same as that of ambient atmospheric pressure of 0.1 MPa; the synthesis temperature of around 110 C thus corresponds to the boiling temperature of high-concentration alkaline solution.

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On the contrary, hydrothermal synthesis using an autoclave, which provides closed reaction environment and hence the slightly higher pressure during the processing, can also be attempted to synthesize TNT [28]. Furthermore, not only TiO2 but also Ti metal can be used as the source material of TNT [29], in which process titanium is chemically oxidized in the alkaline solution. The size control of TNT also has attracted much attention. Various sized, especially thick TNT can often be synthesized by the hydrothermal method, because it gives higher synthesis temperature than 110 C. In addition, natural mineral source is also used for the TNT synthesis that may reduce the production cost of the TNT [30]. X-ray diraction patterns showing phase development during the chemical processing are shown in Fig. 2.1, and corresponding transmission electron micrographs are represented in Fig. 2.2. After alkaline treatment, the product mainly consists of amorphous and crystalline phase corresponding to sodium titanate (Na2 TiO3 , Fig. 2.1b), but the shapeless matter is obtained (Fig. 2.2a). After the water and HCl treatment (Figs. 2.1c and 2.2b), sodium titanate disappears completely and another crystalline phase with low crystallinity is observed. In this step, nanometer-sized sheet-like morphology can be obtained, which is considered as the TiO2 nanosheet. Further, water washing provides brous product (Fig. 2.2c) with the length of several hundreds to several micrometers. Higher magnication TEM photograph shown in Fig. 2.2d clearly reveals that the outer and inner diameter of the nal product is around 810 and 57 nm, respectively, and it has an open-end structure. The size of obtained TNT does not depend on the kind of raw materials used. In addition, when KOH is used as a reaction solution, TNT can also be produced with the similar size and morphology.

Fig. 2.1. X-ray diraction patterns of products obtained in each chemical synthesis step: (a) anatase-type TiO2 raw material, (b) after alkaline reux (10 M NaOH, 110 C, 24 h), (c) after water washing, (d) nal product (after 0.1 M HCl and water washing)

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Fig. 2.2. TEM images showing morphological development of the products in each chemical synthesis step: (a) after alkaline reux (10 M NaOH, 110 C, 24 h), (b) after 0.1 M HCl treatment, (c) nal product, (d) high magnication image of obtained nanotubes

The surface area of the typical TNT is approximately 300 350 m2 /g, and the value is in good agreement with the calculated theoretical surface area, 345 m2 /g, by assuming the tubular structure, the observed size, and the density of TiO2 crystal. However, recent investigation has revealed that the larger TNT with more than 10 nm in diameter can be obtained when larger titanium oxide powders with particle diameter in micrometer is used and when hydrothermal synthesis method is utilized.

2.2.2 Nanostructures and Formation Mechanism On the contrary to layered compounds like graphite, TiO2 has rigid crystal structure in which a lattice spreads out isotropically and three dimensionally, so that its crystal shape is usually equiaxial. However, solution chemical synthesis described above gives anisotropic and open-end nanotube structure in TiO2 . In order to identify the structural characteristic and also to understand the formation mechanism of TNT in relation to its synthesis process, much eorts for the structural analyses have been paid by using X-ray and

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Fig. 2.3. TEM image of TiO2 nanotube bundle (a) and selected area electron diraction pattern (b)

neutron diraction and high-resolution electron microscopy coupled with electron diraction technique [9, 10, 2839]. In the selected area electron diraction (SAED) pattern of TNT bundle (Fig. 2.3), some diraction spots with belt-like spreading are found, which is typically found in a brous compound. As summarized in Table 2.1, the interplanar spacing (d-spacing) of spots a (a ), b (b ), and d (d ) correspond to those of (101), (200), and (100) of typical anatase crystal of TiO2 , respectively [38]. From these facts, it is considered that the TNT basically has the similar crystal structure as the anatase type of TiO2 , and then the longitudinal direction of the nanotube corresponds to the a-axis [(100) direction] while the cross section is parallel to the b-plane [(010) plane] of the anatase crystal. On the other hand, the diraction spot c (c ) provides the d-spacing of 0.87 nm, and corresponds to the broad diraction peak found at 2 of around 9 in the XRD patterns of Fig. 2.1d, and also corresponds to the spacing of 0.88 nm at the wall in Fig. 2.2d. The reection of anatase crystal near to this value is (001) with d = 0.951 nm (Table 2.1); however, there is a slightly large deviation (approximately 8.5%) between these values and hence the spot c(c ) seems not to correspond directly to the (001) of anatase structure. This large interplanar distance is a typical characteristic in titanium oxide nanotube and closely related to the formation of the structures as described in the latter part. Thermogravimetry coupled with mass spectroscopic analysis for the assynthesized TNT exhibited the weight loss continued up to approximately 350 C and detected major species was H2 O. High-temperature XRD results

Table 2.1. Interplanar (d) spacing observed for TiO2 nanotube bundle (Fig. 2.3) and corresponding plane and d-spacing of anatase-type TiO2 Position aa b, b d, d c, c d (nm) 0.37 0.19 0.28 0.87 Anatase TiO2 , hkl/d (nm)JCPDS (101)/0.352 (200)/0.189 (110)/0.268 (001) /0.951

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Fig. 2.4. High-temperature X-ray diraction patterns of synthesized TiO2 nanotubes and corresponding structure change

(Fig. 2.4) demonstrated that the typical diraction peak intensity found at 2 around 9 decreased with increasing in test temperature up to around 400 C, while the peaks corresponding to anatase structure of TiO2 became to be the major crystalline phase and its crystallinity increased above the temperature. Annealing temperature dependency of the specic surface area for pure TNT is summarized in Table 2.2 (see also Fig. 2.8). High surface area was maintained up to around 400 C while sudden decrease occurred above the temperature and then reached to the value approximately 100 m2 /g at an annealing temperature higher than 450 C. From TEM investigation for the annealed TNT, its nanotubular structure was found to be kept up to around 450 C. These facts imply us that the as-synthesized TNT contains some amount of hydroxyl group (OH) and/or structure water (H2 O) and has TiO6 octahedral network structure which is similar to common anatasetype structure of TiO2 crystal or, in another words, has titanate-like structure [38]. By the heat treatment (annealing) for the as-synthesized TNT, proton is released as H2 O and then the nanotube becomes to be the stoichiometric
Table 2.2. Variation of surface area on the annealing temperature for the TiO2 nanotubes. The surface area is measured by the BET method Temperature ( C) Surface area (m2 /g) RT 322 200 308 400 228 450 123 500 101 550 95.0

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Fig. 2.5. (010) projection of H2 Ti3 O7 unit cell (a) and structure model of nanotube by assuming a chemical composition as H2 Ti3 O7 (b and c) proposed by Chen et al. [31]. Reprinted with permission from [31]

TiO2 nanotube with an anatase structure as its base crystal structures at around 400 C. Detailed structure analyses have been carried out extensively. Chen et al. [31] investigated the structure of chemically prepared TNT by using highresolution transmission electron microscopy and reported that the TNT was titanate with the chemical formula of H2 Ti3 O7 and proposed the structure model as shown in Fig. 2.5. On the other hand, Ma et al. [32, 33] showed it was lepidocrocite which was one of the defect-containing titanate with the formula of Hx Ti2x/4 x/4 O4 . Besides these structures, various compositions were reported, Na2 Ti2 O4 (OH)2 or its protonated titanate of H2 Ti2 O4 (OH)2 [34] and H2 Ti4 O9 [35]. These compounds, however, basically contain OH group and/or H2 O and can be described as (TiO2 )n (H2 O)m , which reasonably explains the fact that H2 O is released by the heat treatment of as-synthesized TNT as mentioned above. The reason why many plausible composition models are reported is considered as follows; synthesized TNT usually has a small diameter and hence the wall thickness is quite thin, around 12 nm, and also its crystallinity is rather low as shown in Fig. 2.1 by comparing with usual TiO2 crystalline particles. Furthermore, a large number of titanates are known in the series, and most of them have a layered structure with the similar structure. As mentioned before, TNT can be fabricated by using not only NaOH but also KOH, while the nanotubular matter is not synthesized in the case of LiOH solution; in this case more stable crystalline LiTiO2 is formed [38]. These facts imply us that the formation of alkaline titanate like Na2 TiO3 or its amorphous matter (see Fig. 2.1b) is an important intermediate compound

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for the formation of the nanotube. By considering these facts the formation of the TNT is thus regarded as follows: at rst, titanate-containing alkali metals (alkali titanates) is formed during the solution chemical treatment. Then the alkali metal element is ion exchanged, and protonated titanate is formed as a nanosheet. In the nal step, the nanosheet converts to be a tubular structure (Fig. 2.5) by scrolling process in order to lower the surface energy. Till now a large number of discussions on the actual structure models and formation mechanisms for the TiO2 nanotubes [3739], and related investigations such as process development for controlling nanotubes length and diameter and extended research toward nanowires/nanorods, are continued by many research groups. Nevertheless, it should be noted that the crystal structure based on the three-dimensional framework of TiO6 polyhedron and low-dimensional nanostructure formation for the TiO2 nanotube is a quite unique and dierent from those of the carbon nanotube, which is built from the two-dimensional graphene sheet (carbon network).

2.3 Functions of Titanium Oxide Nanotubes

Similar to common TiO2 powder, the TNT is also white colored powder. The optical bandgap energy calculated from the ultravioletvisible light absorption spectra by assuming indirect transition of TiO2 is approximately 3.41 3.45 eV for chemically synthesized TNT [38], which value is slightly larger than that of anatase (3.2 eV) and rutile (3.0 eV) crystals. This blue shift of the absorption edge wavelength is attributed to the quantum size eect of TiO2 semiconductor [40] in TNT because of very thin nanotube wall thickness of around 1 2 nm. Recent materials design strategy of TiO2 nanoparticles focuses on the developed visible light responsible TiO2 photocatalyst [41] so that the enlarged bandgap seems to be disadvantageous; nevertheless TNT exhibits unique and excellent photochemical properties which contribute enhanced environmental purication performance. 2.3.1 Photochemical Properties and Photocatalytic Functions In order to clarify the photochemical characteristic of TNT, Tachikawa et al. [42] investigated the photocatalytic one-electron oxidation reaction of an organic molecule and related charge recombination dynamics during UV light irradiation on TNT using time-resolved diuse reectance spectroscopy. They observed remarkably long-lived radical cation and trapped e for the TNT, approximately ve times or more long lifetime than those for the nanoparticles. Further, they have observed that the electron generated by the steady-state irradiation of UV light could exist for longer time on the TNT surface, which phenomenon was usually not conrmed in TiO2 nanoparticles, and also the evidence of rapid reaction of trapped e with organic halide pollutants such as CCl4 . These features are considered mainly due to the unique one-dimensional

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nanostructure of the TNT and are the reason of the good photocatalytic properties; TNT has very thin wall so that generated carriers can eectively move to the surface, and then charge recombination is inhibited due to its long one-dimensional structure, clearly suggesting morphological advantage of the TNT on the charge recombination dynamics. These may also be advantageous for the use of TNT as for the electrode of solar cell in which transfer characteristic is very important. In fact, longer lifetime while the similar diusion coecient of electron in TNT has been reported when it has used for the electrode of dye-sensitized solar cell [43]. As mentioned before, anatase-type TiO2 is well known as a promising photocatalytic material due to its photochemical characteristic. Figure 2.6 shows variation of hydrogen generation by UV light irradiation to as-synthesized and annealed TNTs and commercial TiO2 nanoparticles in water/methanol mixed solution (so-called water splitting test) [38]. As can be seen from the gure, as-synthesized TNT shows lower photocatalytic activity than the commercial TiO2 powders (P-25 and ST01). This low activity is considered due to the existence of many hydroxyls (OH) and/or structural water (H2 O) and low crystallinity of the as-synthesized TNT. On the other hand, annealed (400 C) TNT can generate approximately two to three times higher amount of H2 than that of nanoparticles, when compared to H2 amount per unit mass of TiO2 photocatalyst. The enhanced hydrogen evolution performance of the annealed TNT is caused by the improved crystallinity (see Fig. 2.4) with maintaining its nanotubular structure and higher surface area, around 230 m2 /g (Table 2.2 and Fig. 2.8), than that of TiO2 nanoparticle (approximately 50 m2 /g). However, by comparing the generated amount of H2 per unit surface area of the catalysts, TNT exhibits around 4465 % of nanoparticle system. This fact indicates that an approximately half of the surface may not act as for the active site of hydrogen generation, and hence the inner wall of the nanotube

Fig. 2.6. Hydrogen generation by the water splitting during UV irradiation to various TiO2 photocatalysts (P-25 and ST01, commercial TiO2 nanopowders, asprepared TNT, and annealed TNT at 400 C)

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may not contribute to the photocatalytic reaction, which is probably due to the diusion limit of molecules within the inner part of the nanotubes during the reaction. Nevertheless, it is expected that the TNT would be one of the promising candidate as the high-performance energy creation materials and systems such as the excellent hydrogen generation catalyst. 2.3.2 Novel Environmental Purication Functions Photocatalytic performance is often evaluated by the removal test of organic molecules in water system. Figure 2.7 represents the variation of methylene blue (MB) concentration in TiO2 dispersed water system under dark and UV light irradiation conditions. In the case of commercial TiO2 nanoparticles, MB concentration is quickly decreased under UV irradiation while is not changed without the UV irradiation (hence under the dark condition). This clearly indicates that the TiO2 nanopowder is an excellent photocatalyst. However, in the case of as-synthesized TNT, MB decrease can be conrmed even under the dark condition and is enhanced further under the UV light irradiation. This fact indicates that the TNT has a molecule adsorption characteristic, and it is more obvious than the photocatalytic degradation under the UV irradiation. When TNT is annealed, the MB degradation under the dark condition is reduced; however, the photodegradation is higher than that of as-synthesized TNT. It is again considered that the increased crystallinity can enhance its photocatalytic performance. Generally, TiO2 including nanopowder has very low molecule adsorption capability compared to typical adsorbent materials such as zeolite, activated carbon, and clay minerals. Therefore, development of composite materials of TiO2 photocatalyst and some other adsorbents such as mesoporous silica

Fig. 2.7. Variation of methylene blue concentration under the dark and UV light irradiation conditions for the TiO2 nanoparticle, as-synthesized and annealed TiO2 nanotubes dispersed water system, and schematic drawing of adsorption/photochemical behaviors for the TNT

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[44] has been investigated. On the other hand, TNT has not only excellent photocatalytic property but also high capability for the molecule adsorption as a single phase material. This novel multifunctionality, hence the synergy of molecule adsorption and photocatalytic properties, is attributed to its unique crystal and nanostructures as well as materials photochemical characteristic; as described before, TNT has a high surface area and layered compound-like structure such as clay minerals. These structural characteristics might be the reason of the high adsorption capability of the TiO2 nanotube. Therefore, TNT is regarded as a novel multifunctional nanostructured material and then expected to be an excellent candidate as for the advanced high-performance environmental purication system.

2.3.3 Multi-functionalized Titanium Oxide Nanotubes In order to enhance properties and/or to functionalize materials, doping some elements and/or compositing with the other materials is often utilized. For instance, doping to silicon can control its semiconductive properties and hence various devices are widely developed and used. In the case of TiO2 nanotube, these are also applicable techniques. For instance, when TNT is considered to be used as the chemical sensing device, electrode of solar cell, and so on, control and improvement of electrical properties are necessary and required to obtain higher conductivity, i.e., good carrier transfer properties and resultant better device performance. For this purpose, various metal cations have been doped into TNT via the chemical synthesis process [45]. When transition metal cations such as Cr3+ , Mn3+ , Co2+ , Nb5+ , and V5+ were doped, morphology, surface area, and optical bandgap of the doped TNT were almost as same as those of pure TNT. However, electrical conductivity of the doped TNT was around 12 orders of magnitude higher, for example, 1.0 104 S/cm for 0.08 mol% Cr-doped TNT, than those of TiO2 nanopowder (2.6 106 S/cm) or pure TNT (3.0 106 S/cm). Another eect of cation doping to the TNT was found in the thermal stability improvement as shown in Fig. 2.8; structural degradation of the nanotube and the resultant decrease of surface area began at around 400 C for the pure TNT (refer also to Table 2.2). However, the critical temperature was enhanced approximately 50 (Mn3+ , Co2+ , Nb5+ , V5+ ) to 100 C (Cr3+ ) for the doped TNT [38]. These facts indicate that the cation doping can enhance both electrical conductivity and thermal stability of the nanotube, which is regarded as one of the advantages when the TNT will be used as various devices, because most of these devices are fabricated by the pasting and the following sintering of the material to form lms on the appropriate substrates. Furthermore, loading various metals and/or compounds into inside of the nanotubes and/or onto the surfaces in nanometer scale is possible. Figure 2.9 shows TEM images of metals and sulde compound-loaded TNT nanocomposites which were prepared by using various physicochemical processing.

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Fig. 2.8. Temperature dependence of BET surface area of cation-doped TNTs (cation concentration ca. 0.1 mol%) and corresponding morphology change for pure and Cr-doped TNTs at 500 C

Fig. 2.9. Various TNT-metal nanocomposites. (a) Pd-loaded TNT prepared by sonochemical method, (b) Ag nanoparticles formed inside of the TNT, (c) Ni nanoparticles inside of the TNT, (d) ZnS-loaded TNT prepared by solution chemical route

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When Pd nanoparticles are composed with the TNT, hydrogen generation performance was much enhanced due to the promoting eect of the loaded noble metals [38]. For the properties enhancement and further multifunctionalization, nanocompositing of TNT with the other materials is suitable and advantageous method.

2.4 Conclusion and Prospects

In this chapter, chemical processing, structure, physical, and chemical properties of TiO2 nanotube that can be prepared by the solution chemical route have been reviewed. Till now, a large number of fundamental studies and application-oriented researches and developments are extensively carried out by many researchers for this low-dimensional nanomaterial, because not only enhancement of various properties of TiO2 but also multifunctionalization due to the harmonization of materials properties and unique lowdimensional nanostructure is expected. As for the application of TNT, it has been used as the oxide electrode of the dye-sensitized solar cell, and better cell eciency and structure-related characteristics on the charge transport phenomenon have been reported [43]. Also it is reported that TNT exhibits proton intercalation/de-intercalation and resultant electrochromism, size-selective adsorption of molecules [46], anion doping to develop visible light responsible TNTs [47], and biocompatibility [48, 49]. On the other hand, extensive challenges to develop various oxide and compound nanotubes have been continued. For instance, rare earth oxide nanotubes have recently been synthesized [50]. (Details on the variety of nanotube materials are introduced in other chapters.) All these facts imply us that the oxide nanotubes including TNT have multifunctionalities owing to the structureproperty correlations. As mentioned before, one of the future research direction of the TiO2 nanotube might lie toward the application as the environmental and/or energy creating systems, which would become more important in the near future.

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Index
Ag nanoparticles in TNT, 29 Carbon nanotube (CNT) discovery, 17 Cation doping to TNT, 28 Direct synthesis of TNT, 19 Environmental purication functions of TNT, 2728 Formation mechanism of TNT, 2125 High-temperature X-ray diraction patterns of synthesized TNT, 23 Hydrothermal synthesis of TNT, 20 Interplanar spacing in TNT, 22 Kasuga method, 18 Low temperature solution chemical processing synthesis of TNT, 1821 Ni nanoparticles in TNT, 29 Pd-loaded TNT, 29 Photocatalytic functions of TNT, 2527 Photochemical properties of TNT, 2527 Selected area electron diraction (SAED) pattern of TNT, 22 Self-structuralization or selforganization, 18 Surface area variation on annealing temperature for TNT, 23 TEM images of TNT synthesis, 2122 Temperature dependence of BET surface area of cation-doped TNTs, 29 Template or replica method, 18 Titanium oxide nanotube (TNT) mutual and synergy combination, 18 Titanium oxide nanotube (TNT) properties, 18 TNT-metal nanocomposites, 29 Water splitting test, 26 X-ray diraction patterns of TNT synthesis, 20 ZnS-loaded TNT, 29

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