JP2004331490A - Titania nanotube and method for producing the same - Google Patents
Titania nanotube and method for producing the same Download PDFInfo
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Abstract
【課題】
従来のチタニアナノチューブは粉末として取り扱われており、粉末ではなくナノチューブとしての特性を充分引き出せるチタニアナノチューブ、その用途およびその製造方法が求められていた。
【解決手段】
長さが１μｍ以上であることを特徴とするチタニアナノチューブ。前記記載のチタニアナノチューブに電極を設置してなることを特徴とするガスセンサー。前記記載のチタニアナノチューブを用いてなることを特徴とする色素増感太陽電池用電極。前記記載のチタニアナノチューブを用いてなることを特徴とする光触媒。チタニア粉末を６０℃以上の水酸化ナトリウム水溶液中に分散させることを特徴とするチタニアナノチューブの製造方法。
【選択図】 なし
【Task】
Conventional titania nanotubes are handled as powder, and there has been a demand for titania nanotubes that can sufficiently bring out the properties as nanotubes instead of powder, their uses, and methods for producing them.
[Solution]
A titania nanotube having a length of 1 μm or more. A gas sensor comprising an electrode provided on the titania nanotube described above. An electrode for a dye-sensitized solar cell, comprising the titania nanotube described above. A photocatalyst comprising the titania nanotube described above. A method for producing titania nanotubes, comprising dispersing titania powder in an aqueous solution of sodium hydroxide at 60 ° C. or higher.
[Selection diagram] None
Description
本発明は、１μｍ以上の長さを有するチタニアナノチューブおよびその製造方法に関する。 The present invention relates to a titania nanotube having a length of 1 μm or more and a method for producing the same.
カーボンナノチューブが発見されて以来、種々の物質についてナノチューブの製造可能性が検討されており、チタニア（ＴｉＯ2）のナノチューブが生成することが知られている。チタニアは光触媒活性があり、チタニアナノチューブはチタニア粉末より高い触媒活性を有することが期待されている。 Since the discovery of carbon nanotubes, the possibility of producing nanotubes for various substances has been studied, and it is known that titania (TiO 2 ) nanotubes are produced. Titania has photocatalytic activity, and titania nanotubes are expected to have higher catalytic activity than titania powder.
チタニアナノチューブとしては、直径５〜８０ｎｍ、長さ５０〜１５０ｎｍのものが知られており、その製造方法としては、平均粒径１５ｎｍのチタニア粉末を出発原料とし、濃度１５〜６５重量％の水酸化ナトリウム水溶液中にチタニア粉末を分散させずに浸漬し、密閉容器内で２０〜１５０℃に加熱する方法が提案されている（例えば、特許文献１参照）。 As the titania nanotubes, those having a diameter of 5 to 80 nm and a length of 50 to 150 nm are known. As a production method, titania powder having an average particle size of 15 nm is used as a starting material, and a hydroxide having a concentration of 15 to 65% by weight. A method has been proposed in which titania powder is immersed in a sodium aqueous solution without being dispersed, and heated to 20 to 150 ° C. in a closed container (for example, see Patent Document 1).
しかし、従来のチタニアナノチューブは長さが１５０ｎｍ程度のものしか知られておらず、粉末ではなくナノチューブとしての特性を十分引き出せるものではなかった。 However, conventional titania nanotubes are known only to have a length of about 150 nm, and have not been able to sufficiently bring out the properties of nanotubes, not powder.
このような状況に鑑み、本発明者らは、いかなるチタニアナノチューブがナノチューブとしての特性を十分引き出せるものであるかについて、そして、ナノチューブとしての特性を十分引き出した用途について鋭意検討し、その結果、チタニアナノチューブの長さを１μｍ以上の長さとすることにより、光センサーおよびガスセンサー等として利用できることに思い至った。 In view of such a situation, the present inventors have eagerly studied what titania nanotubes can sufficiently bring out the properties as nanotubes, and about applications in which the properties as nanotubes are sufficiently drawn out. By setting the length of the nanotube to 1 μm or more, the inventors came to realize that the nanotube can be used as an optical sensor, a gas sensor, and the like.
さらに、本発明者らは、かかるチタニアナノチューブの製造方法についても鋭意検討した結果、従来のチタニアナノチューブの製造方法においては、チタニアナノチューブが破損しないよう撹拌や振動を避けて水酸化ナトリウム水溶液中に出発原料のチタニア粉末を浸漬することにより行われていたのに対して、驚くべきことに、１μｍ以上の長さのチタニアナノチューブは、チタニア粉末を一定温度範囲の水酸化ナトリウム水溶液中に撹拌等により分散させることにより製造できることを見出し、本発明を完成させるに至った。 Furthermore, the present inventors have conducted intensive studies on such a method for producing titania nanotubes.As a result, in the conventional method for producing titania nanotubes, starting in an aqueous sodium hydroxide solution, avoiding stirring or vibration so that the titania nanotubes are not damaged. Surprisingly, the titania nanotubes having a length of 1 μm or more are dispersed in a sodium hydroxide aqueous solution within a certain temperature range by stirring or the like, whereas the titania powder used as a raw material is immersed in the titania powder. The present invention was found to be able to be produced by the above-mentioned process, and the present invention was completed.
すなわち本発明は、長さが１μｍ以上であることを特徴とするチタニアナノチューブを提供する。また本発明は、チタニアナノチューブに電極を配設してなることを特徴とするガスセンサーを提供する。さらに本発明は、チタニア粉末を水酸化ナトリウム水溶液中に分散させることを特徴とするチタニアナノチューブの製造方法を提供する。 That is, the present invention provides a titania nanotube having a length of 1 μm or more. Further, the present invention provides a gas sensor comprising an electrode disposed on a titania nanotube. Further, the present invention provides a method for producing titania nanotubes, comprising dispersing titania powder in an aqueous sodium hydroxide solution.
本発明の製造方法により長さ１μｍ以上のチタニアナノチューブを製造することができ、長さ１μｍ以上の本発明のチタニアナノチューブは、従来のチタニアナノチューブでは用いることができなかったセンサー用、色素増感太陽電池用電極用、光触媒用、金属材料や樹脂材料の強化材用として好適に用いることができるので、本発明は工業的に極めて有用である。 The titania nanotube having a length of 1 μm or more can be produced by the production method of the present invention, and the titania nanotube of the present invention having a length of 1 μm or more can be used as a dye-sensitized solar cell for a sensor which cannot be used with a conventional titania nanotube. The present invention is industrially extremely useful because it can be suitably used as a battery electrode, a photocatalyst, and a reinforcing material for a metal material or a resin material.
本発明のチタニアナノチューブは、その長さが１μｍ以上である。長さが１μｍ以上であることにより、両端に電極を設置することが可能となり、センサーとして利用することが可能となる。チタニアナノチューブの長さが長い方が取扱いや加工が容易となるので、１０μｍ以上が好ましく、１００μｍ以上がさらに好ましい。より具体的には、光センサー（紫外線センサー、赤外線センサー、可視光センサー）として用いることができ、さらにガスセンサーとして用いることができる。チタニアは光によりその導電性が変化するので、その変化を測定することにより、紫外線センサー、赤外線センサー、可視光センサーとして用いることができる。また、チタニアナノチューブのチューブ内に特定の気体の分子が吸着されることによりチタニアナノチューブの導電性が変化するので、ガスセンサーとして用いることができる。
なお、電極は通常は、金、白金または銀製の線を接続して設置することができる。
The length of the titania nanotube of the present invention is 1 μm or more. When the length is 1 μm or more, electrodes can be provided at both ends, and can be used as a sensor. A longer length of the titania nanotubes facilitates handling and processing. Therefore, the length is preferably 10 μm or more, and more preferably 100 μm or more. More specifically, it can be used as a light sensor (ultraviolet light sensor, infrared light sensor, visible light sensor), and can be used as a gas sensor. Since the conductivity of titania changes with light, by measuring the change, it can be used as an ultraviolet sensor, an infrared sensor, or a visible light sensor. In addition, a specific gas molecule is adsorbed in the titania nanotube tube to change the conductivity of the titania nanotube, so that the titania nanotube can be used as a gas sensor.
The electrodes can be usually installed by connecting gold, platinum or silver wires.
また、本発明のチタニアナノチューブは、高い効率を示す色素増感太陽電池を与える電極に用いることができる。
色素増感太陽電池用電極は多孔質膜からなり、従来のチタニア粉末を用いてなる多孔質膜を電極として用いた場合、チタニア粒子の間の粒界およびネッキング部分表面において、電子とホールの再結合、逆電子移動（電解液への漏れ）、ネッキング部分表面に生じる表面準位による電子のトラップ、粒界に生じる粒界準位による電子のトラップなどにより、光励起により色素から電極に注入された電子のうち、色素増感太陽電池の発電効率に寄与しない電子が生じ、色素増感太陽電池の効率を下げていることが知られている。これに対し、長さが１μｍ以上と長く、粒界やネック部分がない本発明のチタニアナノチューブからなる電極は、高い効率を示す色素増感太陽電池を与え得る。
Further, the titania nanotube of the present invention can be used as an electrode for providing a dye-sensitized solar cell exhibiting high efficiency.
Dye-sensitized solar cell electrodes are made of a porous film, and when a porous film made of conventional titania powder is used as the electrode, electrons and holes are regenerated at the grain boundaries between titania particles and on the surface of the necking portion. Electrons were injected from the dye into the electrode by photoexcitation due to binding, reverse electron transfer (leakage into the electrolyte), electron trapping due to surface levels occurring at the necking part surface, and electron trapping due to grain boundary levels occurring at grain boundaries. It is known that among the electrons, electrons that do not contribute to the power generation efficiency of the dye-sensitized solar cell are generated, thereby lowering the efficiency of the dye-sensitized solar cell. On the other hand, an electrode comprising the titania nanotube of the present invention having a length as long as 1 μm or more and having no grain boundary or neck portion can provide a dye-sensitized solar cell exhibiting high efficiency.
本発明のチタニアナノチューブを用いてなる色素増感太陽電池用電極は、次のようにして製造することができる。本発明のチタニアナノチューブを水また有機溶媒中に分散させてスラリーとし、透明導電性膜付きガラスの上に塗布して乾燥させた後、電気炉などを用いて焼成し、チタニアナノチューブからなる多孔質膜を透明電極上に作製する。得られた多孔質膜に色素を吸着させ、乾燥させて色素増感太陽電池用電極を製造することができる。そして、この電極と、スパッタリングにより白金で被覆した対極とをセル内に設置し、ヨウ素などを含む電解液を封入することにより、色素増感太陽電池を作製することができる。 The electrode for a dye-sensitized solar cell using the titania nanotube of the present invention can be manufactured as follows. The titania nanotubes of the present invention are dispersed in water or an organic solvent to form a slurry, coated on a glass with a transparent conductive film, dried and then fired using an electric furnace or the like to form a porous layer of the titania nanotubes. A film is made on a transparent electrode. A dye is adsorbed on the obtained porous film and dried to produce a dye-sensitized solar cell electrode. Then, this electrode and a counter electrode coated with platinum by sputtering are placed in a cell, and an electrolyte containing iodine or the like is sealed, whereby a dye-sensitized solar cell can be manufactured.
また、本発明のチタニアナノチューブは、比表面積が５０ｍ2／ｇ以上と大きいので、光触媒用に好適である。光触媒は、油脂の光による分解を生じさせることが知られており、光触媒は、付着する油脂汚れを光の照射により分解除去して物体表面を清浄に保つことができる防汚膜用として、防汚膜に含有させて用いられている。本発明のチタニアナノチューブを含有してなる光触媒は、水また有機溶媒中に分散させてスラリーとし、防汚対象の物体の表面に塗布して、防汚膜として用いることができる。 In addition, the titania nanotube of the present invention has a large specific surface area of 50 m 2 / g or more, and thus is suitable for use as a photocatalyst. Photocatalysts are known to cause the decomposition of fats and oils by light. Photocatalysts are used as antifouling films for decomposing and removing adhering fats and oils by irradiating light to keep the object surface clean. It is used by being contained in a soil film. The photocatalyst containing the titania nanotube of the present invention can be used as an antifouling film by dispersing it in water or an organic solvent to form a slurry, applying the slurry on the surface of an object to be antifouled.
また、チタニアナノチューブは強度が高いものと推定されるので、長さが１μｍ以上である本発明のチタニアナノチューブは、金属材料や樹脂材料に混合して強化材として用いることもできる。 Since the titania nanotube is presumed to have high strength, the titania nanotube of the present invention having a length of 1 μm or more can be mixed with a metal material or a resin material and used as a reinforcing material.
なお、本発明のチタニアナノチューブは、その直径が０．１μｍ以下であるものが好ましい。直径が０．１μｍ以下であれば、比表面積が大きく、光またはガスによりチタニアナノチューブの表面または内面が変化することにより導電性が変化し、その導電性の変化を検出するセンサーに用いた場合、感度が高くなるので好ましい。さらに、本発明のチタニアナノチューブは、そのアスペクト比が１００以上であるものがより好ましい。アスペクト比は、物体の長軸方向の長さを最大幅（横断面が円形であれば直径）で除した値である。 The titania nanotube of the present invention preferably has a diameter of 0.1 μm or less. If the diameter is 0.1μm or less, the specific surface area is large, the conductivity changes by changing the surface or inner surface of the titania nanotube by light or gas, when used for a sensor that detects the change in conductivity, It is preferable because the sensitivity is increased. Further, the titania nanotube of the present invention preferably has an aspect ratio of 100 or more. The aspect ratio is a value obtained by dividing the length in the major axis direction of the object by the maximum width (the diameter if the cross section is circular).
次に、長さが１μｍ以上の本発明のチタニアナノチューブを製造する方法を説明する。
本発明の製造方法においては、チタニア粉末を出発原料として用い、チタニア粉末を水酸化ナトリウム水溶液中に分散させる。チタニア粉末を水酸化ナトリウム水溶液中に浸漬し、６０℃以上の温度にしただけでは本発明のチタニアナノチューブは生成せず、分散させる必要がある。分散方法としては、チタニア粉末を含む水酸化ナトリウム水溶液を撹拌してもよいし、超音波などにより分散させてもよいし、これらを組み合わせてもよい。分散が十分でない場合はチタニアナノチューブが生成しないおそれがある。撹拌や超音波による分散は、十分に分散させたあと止めることもでき、水酸化ナトリウム水溶液中での加熱の間続けることもできる。
Next, a method for producing the titania nanotube of the present invention having a length of 1 μm or more will be described.
In the production method of the present invention, titania powder is used as a starting material, and the titania powder is dispersed in an aqueous sodium hydroxide solution. Simply immersing the titania powder in an aqueous solution of sodium hydroxide and raising the temperature to 60 ° C. or higher does not produce the titania nanotubes of the present invention, but needs to be dispersed. As a dispersion method, an aqueous sodium hydroxide solution containing titania powder may be stirred, may be dispersed by ultrasonic waves or the like, or may be combined. If the dispersion is not sufficient, titania nanotubes may not be generated. Dispersion by stirring or ultrasonic waves can be stopped after sufficient dispersion, or can be continued during heating in an aqueous sodium hydroxide solution.
チタニア粉末はルチル型であってもアナターゼ型であってもよい。チタニア粉末は微粒の粉末を用いることが好ましく、具体的には、平均粒径が５０ｎｍ以下のものが好ましく、平均粒径２０ｎｍ以下のものがより好ましく、１０ｎｍ以下のものがさらに好ましい。平均粒径は、粉末の真密度（ｇ／ｃｍ3）とＢＥＴ比表面積（ｍ2／ｇ）とから、６／［ＢＥＴ比表面積×真密度］により算出されるＢＥＴ径（μｍ）として求めることができる。 The titania powder may be rutile or anatase. As the titania powder, it is preferable to use fine powder. Specifically, the powder having an average particle diameter of 50 nm or less is preferable, the powder having an average particle diameter of 20 nm or less is more preferable, and the powder having an average particle diameter of 10 nm or less is further preferable. The average particle size is determined as a BET diameter (μm) calculated from 6 / [BET specific surface area × true density] from the true density (g / cm 3 ) and the BET specific surface area (m 2 / g) of the powder. Can be.
チタニア粉末を分散させる水酸化ナトリウム水溶液中の水酸化ナトリウムの濃度は、１Ｍ（モル／リットル）以上１５Ｍ以下が好ましく、３Ｍ以上１３Ｍ以下がより好ましく、７Ｍ以上１２Ｍ以下がさらに好ましい。水酸化ナトリウムの濃度が低すぎる場合または高すぎる場合は、本発明のチタニアナノチューブが生成しないおそれがある。 The concentration of sodium hydroxide in the aqueous sodium hydroxide solution in which the titania powder is dispersed is preferably 1 M (mol / L) or more and 15 M or less, more preferably 3 M or more and 13 M or less, and even more preferably 7 M or more and 12 M or less. If the concentration of sodium hydroxide is too low or too high, the titania nanotube of the present invention may not be produced.
水酸化ナトリウム水溶液の温度は６０℃以上であり、９０℃以上１２０℃以下が好ましく、１００℃以上１２０℃以下がさらに好ましい。チタニア粉末を水酸化ナトリウム水溶液中に分散させる時間は、通常は１〜５０時間程度である。 The temperature of the aqueous sodium hydroxide solution is 60 ° C or higher, preferably 90 ° C or higher and 120 ° C or lower, more preferably 100 ° C or higher and 120 ° C or lower. The time for dispersing the titania powder in the aqueous sodium hydroxide solution is usually about 1 to 50 hours.
水酸化ナトリウム水溶液中のチタニア粉末の量は、水酸化ナトリウム水溶液１００重量部に対して０．０１重量％以上０．１重量％以下が好ましく、０．０１重量部以上０．０４重量部以下の範囲がさらに好ましい。０．０１重量％未満であると、チタニア粉末が水酸化ナトリウム水溶液に溶解して消失するおそれがあり、０．１重量％を超えると、本発明のチタニアナノチューブが得られないおそれがある。 The amount of the titania powder in the aqueous sodium hydroxide solution is preferably 0.01% by weight or more and 0.1% by weight or less, more preferably 0.01% by weight or more and 0.04% by weight or less based on 100% by weight of the aqueous solution of sodium hydroxide. The range is more preferred. If it is less than 0.01% by weight, the titania powder may be dissolved in an aqueous sodium hydroxide solution and disappear, and if it exceeds 0.1% by weight, the titania nanotube of the present invention may not be obtained.
チタニア粉末を分散させた水酸化ナトリウム水溶液の容器は、開放容器でもよいし、密閉容器でもよい。水酸化ナトリウム水溶液の水の蒸気圧が低い条件で行うときは水の蒸発はあまり起こらないので、大気開放容器でもよいが、水酸化ナトリウム水溶液の水の蒸気圧が高い条件において大気開放で行うときは水の蒸発により水の減少が起こるので還流などにより蒸発した水を戻してやる必要がある。さらに水酸化ナトリウム水溶液の水の蒸気圧が高い条件で行うときは、オートクレーブなどの耐圧の密閉容器内で行うことが望ましい。 The container of the aqueous sodium hydroxide solution in which the titania powder is dispersed may be an open container or a closed container. When performing under conditions where the vapor pressure of the aqueous sodium hydroxide solution is low, water evaporation does not occur very much, so the container may be open to the atmosphere. Since water decreases due to evaporation of water, it is necessary to return water evaporated by reflux or the like. Further, when the reaction is carried out under the condition that the vapor pressure of the aqueous sodium hydroxide solution is high, it is desirable to carry out the treatment in a pressure-resistant closed vessel such as an autoclave.
チタニア粉末を水酸化ナトリウム水溶液に分散させている間の気圧は特に限定されないが、常圧（０．０８ＭＰａ〜０．１２ＭＰａ）または耐圧の密閉容器内で加圧（０．１２ＭＰａ以上）で行ってもよい。減圧（０．０８ＭＰａ未満）で行うときは、水が蒸発するので還流させて水を戻すなどの工夫が必要になる。（変更していません。） The atmospheric pressure during the dispersion of the titania powder in the aqueous sodium hydroxide solution is not particularly limited, but the atmospheric pressure (0.08 MPa to 0.12 MPa) or the pressurization (0.12 MPa or more) in a pressure-resistant closed container is used. Is also good. When the operation is performed under reduced pressure (less than 0.08 MPa), it is necessary to take measures such as refluxing and returning the water because the water evaporates. (Not changed.)
チタニア粉末を水酸化ナトリウム水溶液に分散させて、６０℃以上の温度にした後は、室温まで冷却した後、得られた固体を水酸化ナトリウム水溶液から濾過やデカンテーション等の方法により取り出し、洗浄することが好ましい。希塩酸、希硝酸などの希薄な酸で残留水酸化ナトリウムを中和してから水で洗浄することがさらに好ましい。また、得られた固形分を十分乾燥した後、大気中などで加熱してチタニアナノチューブの結晶性を上げることもできる。 After dispersing the titania powder in an aqueous sodium hydroxide solution and raising the temperature to 60 ° C. or higher, the resultant solid is cooled to room temperature, and the obtained solid is removed from the aqueous sodium hydroxide solution by a method such as filtration or decantation and washed. Is preferred. More preferably, the residual sodium hydroxide is neutralized with a dilute acid such as dilute hydrochloric acid or dilute nitric acid and then washed with water. Further, after sufficiently drying the obtained solid content, the solid content of the titania nanotube can be increased by heating in the air or the like.
このようにして製造された本発明のチタニアナノチューブは、長さが１μｍ以上であり、両端に電極を設置することによりセンサーとして好適に用いることができる。また、本発明のチタニアナノチューブは、樹脂材料や金属材料に混合して強化材料としても好適に用いることができる。さらに、光触媒、色素増感太陽電池用電極、紫外線吸収・遮蔽剤、日焼け止め剤、光電池用材料、導電性フィラー、骨充填材等の用途にも用いることができる。 The titania nanotube of the present invention thus manufactured has a length of 1 μm or more, and can be suitably used as a sensor by providing electrodes at both ends. Further, the titania nanotube of the present invention can be suitably used as a reinforcing material by mixing with a resin material or a metal material. Furthermore, it can also be used for applications such as photocatalysts, dye-sensitized solar cell electrodes, ultraviolet absorbing and shielding agents, sunscreen agents, photovoltaic cell materials, conductive fillers, bone fillers and the like.
以下、本発明を実施例により説明するが、本発明はこれらによって限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
実施例１
濃度１０モル／リットルの水酸化ナトリウム水溶液１００重量部と市販のチタニア粉末（テイカ製、ルチル型、平均粒径１０ｎｍ）を０．０１８７重量部とをＰＴＦＥ製の容器に入れた。マグネチックスターラーにより撹拌しながら１１０℃まで加熱し、１１０℃で２０時間保持してアルカリ処理を行った。容器内の固体を遠心沈降管に移し、遠心沈降により固体を沈め、上澄み液を廃棄した。蒸留水を注いでから遠心沈降を行い、固体を洗浄した。蒸留水による洗浄を繰り返した後に、固体に０．１Ｎの硝酸を注いで洗浄し、さらに蒸留水を注いで上澄み液のｐＨが７となるまで洗浄を繰り返した。得られた固体を乾燥させ、ＳＥＭ（日立製作所製、Ｓ−５１０型）およびＴＥＭ（日立製作所製、Ｈ−９０００型）により観察した結果、長さが最大で約１２０μｍ、直径が５０ｎｍ（アスペクト比は２４００）のチタニアナノチューブが生成していた。得られた固体にはチタニア粒子が混入していたが、チタニアナノチューブの生成量は得られた固体のうちの９割以上であり、また得られた固体の全重量は、出発原料のチタニア粉末の約９割であった。また、得られたチタニアナノチューブのＢＥＴ比表面積は、２０７ｍ2／ｇと大きい値を示した。
Example 1
100 parts by weight of an aqueous solution of sodium hydroxide having a concentration of 10 mol / liter and 0.0187 parts by weight of a commercially available titania powder (manufactured by Teica, rutile type, average particle size: 10 nm) were placed in a PTFE container. The mixture was heated to 110 ° C. while being stirred by a magnetic stirrer, and kept at 110 ° C. for 20 hours to perform an alkali treatment. The solid in the container was transferred to a centrifugal sedimentation tube, the solid was submerged by centrifugal sedimentation, and the supernatant was discarded. After pouring distilled water, centrifugal sedimentation was performed to wash the solid. After repeating the washing with distilled water, the solid was washed by pouring 0.1 N nitric acid, and further, by pouring distilled water, and the washing was repeated until the pH of the supernatant became 7. The obtained solid was dried and observed with a SEM (S-510, manufactured by Hitachi, Ltd.) and a TEM (H-9000, manufactured by Hitachi, Ltd.). Was 2400). Although the obtained solid was mixed with titania particles, the amount of titania nanotubes generated was 90% or more of the obtained solid, and the total weight of the obtained solid was the same as that of the starting material titania powder. It was about 90%. Further, the BET specific surface area of the obtained titania nanotube showed a large value of 207 m 2 / g.
実施例２
出発原料のチタニア粉末として、アナターゼ型のチタニア粉末（石原産業製、平均粒径６ｎｍ）を用いた以外は実施例１と同様にして実施した。ＳＥＭにより観察した結果、長さが最大で約５０μｍ、直径が５０ｎｍ（アスペクト比は１０００）のチタニアナノチューブが生成していた。
Example 2
The procedure was performed in the same manner as in Example 1 except that anatase-type titania powder (manufactured by Ishihara Sangyo, average particle size: 6 nm) was used as the starting material titania powder. Observation by SEM revealed that titania nanotubes having a maximum length of about 50 μm and a diameter of 50 nm (aspect ratio: 1000) were formed.
比較例１
撹拌を行なわず分散させずに浸漬した以外は実施例１と同様の操作を行った。得られた固体は粒子状であり、チタニアナノチューブは生成しなかった。
Comparative Example 1
The same operation as in Example 1 was performed except that the immersion was carried out without dispersion without stirring. The obtained solid was in the form of particles, and no titania nanotubes were formed.
比較例２
水酸化ナトリウムの代わりに水酸化カリウムを用いた以外は実施例１と同様の操作を行った。得られた固体は粒子状であり、チタニアナノチューブは生成しなかった。
Comparative Example 2
The same operation as in Example 1 was performed except that potassium hydroxide was used instead of sodium hydroxide. The obtained solid was in the form of particles, and no titania nanotubes were formed.
Claims (12)
The method according to any one of claims 7 to 11, wherein the aqueous sodium hydroxide solution in which the titania powder is dispersed is heated to a temperature of 90C or more and 120C or less.
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