JP2009227515A - Method for producing titanium oxide particle and titanium oxide particle - Google Patents
Method for producing titanium oxide particle and titanium oxide particle Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 142
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000002245 particle Substances 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 150000003608 titanium Chemical class 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 70
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical group Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 36
- 239000011780 sodium chloride Substances 0.000 claims description 35
- 238000002441 X-ray diffraction Methods 0.000 claims description 16
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 16
- 150000008045 alkali metal halides Chemical class 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 7
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 31
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 16
- 239000000243 solution Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ROZPZBUZWPOKFI-UHFFFAOYSA-M [Cl-].[Fr+] Chemical compound [Cl-].[Fr+] ROZPZBUZWPOKFI-UHFFFAOYSA-M 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- -1 titanium salt Chemical class 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、光触媒として用いられる酸化チタン粒子の製造方法及び酸化チタン粒子に関する。 The present invention relates to a method for producing titanium oxide particles used as a photocatalyst and titanium oxide particles.
酸化チタン光触媒は、紫外線を照射することで、酸化活性と超親水性の表面特性を発現し、殺菌、防汚、防曇、空気浄化用の材料として、様々な分野への応用研究が進められている。 Titanium oxide photocatalysts exhibit oxidation activity and super hydrophilic surface properties when irradiated with ultraviolet rays, and are being applied in various fields as materials for sterilization, antifouling, antifogging, and air purification. ing.
しかし、酸化チタン光触媒の反応機構上、一つの光触媒粒子で、酸化反応と還元反応という正反対の反応が進行する。そのため、容易に逆反応が起こり、反応効率が激的に減少する。よって、反応場の制御が必要となる。 However, due to the reaction mechanism of the titanium oxide photocatalyst, the opposite reaction of oxidation reaction and reduction reaction proceeds with one photocatalyst particle. Therefore, the reverse reaction easily occurs and the reaction efficiency is drastically reduced. Therefore, it is necessary to control the reaction field.
非特許文献１及び非特許文献２には、ルチル型の外部表面は通常（１１０）面と（０１１）で構成されており、（１１０）面が還元サイトとして、（０１１）面が酸化サイトとして作用することが記載されている。また、アナターゼ型の外部表面は通常（１１０）面と（００１）面で構成されており、（１１０）面が還元サイトとして、（００１）面が酸化サイトとして作用することが記載されている。 In Non-Patent Document 1 and Non-Patent Document 2, a rutile-type external surface is usually composed of (110) plane and (011), (110) plane is a reduction site, and (011) plane is an oxidation site. It is described to work. Further, it is described that the anatase-type external surface is usually composed of a (110) plane and a (001) plane, with the (110) plane acting as a reduction site and the (001) plane acting as an oxidation site.
そして、酸化チタンの還元サイトと酸化サイトを分離して、反応効率を向上させるためには、酸化チタンの結晶構造及び結晶形態の制御が不可欠となる。 In order to improve the reaction efficiency by separating the reduction site and the oxidation site of titanium oxide, it is essential to control the crystal structure and crystal form of titanium oxide.
酸化チタンの結晶構造や結晶形態の制御を行う先行技術としては、例えば、特開２００７−３２０８２１号公報（特許文献１）には、ペルオキソチタン酸及び酸化チタンコロイドと、３Ａ族、５Ａ族、３Ｂ族、４Ｂ族からなる群から選ばれる少なくとも１種のドーピング材用化合物（例えば、塩化ニオブ、塩化タンタル、硫酸バナジル）との混合水溶液を、アルカリ存在下に１１０〜２７０℃の範囲で水熱処理し、次いで、還元ガス雰囲気、酸化ガス雰囲気又は不活性ガス雰囲気下、１００〜７００℃で加熱処理することにより、繊維状あるいは管状の導電性酸化チタンが得られる旨が開示されている。 As a prior art for controlling the crystal structure and crystal form of titanium oxide, for example, Japanese Patent Application Laid-Open No. 2007-320821 (Patent Document 1) includes peroxotitanic acid and a titanium oxide colloid, a group 3A, a group 5A, and a group 3B. Hydrothermal treatment of a mixed aqueous solution with at least one compound for doping material (for example, niobium chloride, tantalum chloride, vanadyl sulfate) selected from the group consisting of Group 4B and Group 4B in the range of 110 to 270 ° C. in the presence of alkali. Then, it is disclosed that fibrous or tubular conductive titanium oxide can be obtained by heat treatment at 100 to 700 ° C. in a reducing gas atmosphere, an oxidizing gas atmosphere or an inert gas atmosphere.
また、特開２００７−１０６６４６号公報（特許文献２）には、三塩化チタンとドデシル硫酸ナトリウムの水溶液を用い、１００〜２３０℃の温度に加熱し、水熱合成により、八面体形体のアナターゼ型粒子が得られる旨が開示されている。 In addition, JP 2007-106646 A (Patent Document 2) uses an aqueous solution of titanium trichloride and sodium dodecyl sulfate, heats it to a temperature of 100 to 230 ° C., and hydrothermally synthesizes an anatase type of octahedral shape. It is disclosed that particles are obtained.
しかし、上記特許文献１は、導電性酸化チタンに関するものであるため、光触媒活性については記載されておらず、どのような手段により光触媒活性の高い酸化チタンが得られるかについては記載されていない。また、上記特許文献２でも、特許文献２の酸化チタンが、光触媒等への幅広い応用が可能であるとのような、一般的な酸化チタンに関する記載があるのみで、どのような手段により光触媒活性の高い酸化チタンが得られるかについては記載されていない。 However, since the said patent document 1 is related to electroconductive titanium oxide, it does not describe about photocatalytic activity, and does not describe what means can obtain titanium oxide with high photocatalytic activity. Further, even in the above-mentioned Patent Document 2, there is only a description relating to general titanium oxide such that the titanium oxide of Patent Document 2 can be widely applied to a photocatalyst or the like. It is not described whether high titanium oxide can be obtained.
よって、上記特許文献１及び２には、光触媒活性の向上という観点から、酸化チタンの結晶構造及び結晶形態の制御を行う手段については開示されていない。 Therefore, Patent Documents 1 and 2 do not disclose means for controlling the crystal structure and crystal form of titanium oxide from the viewpoint of improving the photocatalytic activity.
従って、本発明の課題は、光触媒活性の高い酸化チタンを提供することにある。また、本発明の課題は、光触媒活性を高くするために、酸化チタンの結晶構造及び結晶形態の制御が可能な酸化チタン粒子の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide titanium oxide having high photocatalytic activity. Moreover, the subject of this invention is providing the manufacturing method of the titanium oxide particle which can control the crystal structure and crystal form of a titanium oxide in order to make photocatalytic activity high.
本発明者らは、上記従来技術における課題を解決すべく、鋭意研究を重ねた結果、（１）アルカリ金属の塩化物等のハロゲン化物を、チタン塩水溶液中に存在させて、該チタン塩水溶液を水熱処理することにより、光触媒活性が高い酸化チタンが得られること、（２）特に、該アルカリ金属のハロゲン化物として、塩化ナトリウムを用いることにより、酸化チタンの結晶構造及び結晶形態が制御でき、光触媒活性が高い酸化チタンが得られること、（３）酸化チタンの結晶構造を特定の範囲とすることにより、光触媒活性が高くなること、等を見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the problems in the prior art, the present inventors have made (1) a halide such as an alkali metal chloride in the titanium salt aqueous solution, and the titanium salt aqueous solution. The titanium oxide having a high photocatalytic activity can be obtained by hydrothermal treatment of (2). In particular, by using sodium chloride as the alkali metal halide, the crystal structure and crystal form of titanium oxide can be controlled, The inventors have found that titanium oxide having high photocatalytic activity can be obtained, and (3) that the photocatalytic activity can be increased by setting the crystal structure of titanium oxide within a specific range, thereby completing the present invention.
すなわち、本発明（１）は、アルカリ金属のハロゲン化物を含有するチタン塩水溶液を、水熱処理し、酸化チタン粒子を生成させることを特徴とする酸化チタン粒子の製造方法を提供するものである。 That is, the present invention (1) provides a method for producing titanium oxide particles, characterized in that a titanium salt aqueous solution containing an alkali metal halide is hydrothermally treated to produce titanium oxide particles.
また、本発明（２）は、ミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）が、０．２９〜１．３であることを特徴とする酸化チタン粒子を提供するものである。 In the present invention (2), the X-ray diffraction intensity ratio of the (002) plane to the (110) plane ((002) plane / (110) plane) in the Miller index display is 0.29 to 1.3. Titanium oxide particles characterized by the above are provided.
本発明によれば、光触媒活性の高い酸化チタンを提供することができる。また、本発明によれば、光触媒活性を高くするために、酸化チタンの結晶構造及び結晶形態の制御が可能な酸化チタン粒子の製造方法を提供することができる。 According to the present invention, titanium oxide having high photocatalytic activity can be provided. Moreover, according to this invention, in order to make photocatalytic activity high, the manufacturing method of the titanium oxide particle which can control the crystal structure and crystal form of a titanium oxide can be provided.
本発明の酸化チタン粒子の製造方法は、アルカリ金属のハロゲン化物を含有するチタン塩水溶液を、水熱処理し、酸化チタン粒子を生成させる酸化チタン粒子の製造方法である。 The method for producing titanium oxide particles of the present invention is a method for producing titanium oxide particles in which a titanium salt aqueous solution containing an alkali metal halide is hydrothermally treated to produce titanium oxide particles.
本発明の酸化チタン粒子の製造方法に係る該チタン塩水溶液は、チタン塩の水溶液であり、該チタン塩としては、三塩化チタン、四塩化チタン等の塩化チタン、硫酸チタニル、ペルオキソチタン酸等が挙げられる。これらのうち、酸化チタン粒子の光触媒活性が高くなる点で、塩化チタンが好ましく、三塩化チタンが特に好ましい。 The titanium salt aqueous solution according to the method for producing titanium oxide particles of the present invention is an aqueous solution of a titanium salt. Examples of the titanium salt include titanium chloride such as titanium trichloride and titanium tetrachloride, titanyl sulfate, peroxotitanic acid and the like. Can be mentioned. Among these, titanium chloride is preferable and titanium trichloride is particularly preferable in that the photocatalytic activity of the titanium oxide particles is high.
本発明の酸化チタン粒子の製造方法に係る該アルカリ金属のハロゲン化物として、アルカリ金属の塩化物が挙げられ、具体的には、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化ルビジウム、塩化セシウム、塩化フランシウムが挙げられる。これらのうち、結晶相がルチル型単相の柱状の酸化チタンが得られ、酸化チタン粒子の光触媒活性が高くなる点で、塩化ナトリウムが好ましい。 Examples of the alkali metal halide according to the method for producing titanium oxide particles of the present invention include alkali metal chlorides, specifically, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, and francium chloride. Is mentioned. Of these, sodium chloride is preferable in that a columnar titanium oxide having a rutile-type crystal phase is obtained and the photocatalytic activity of the titanium oxide particles is increased.
該チタン塩水溶液は、該アルカリ金属のハロゲン化物と共に、水溶性高分子を含有することができる。該水溶性高分子としては、例えば、ポリビニルアルコール、ポリビニルピロリドン、メチルセルロース、ヒドロキシルプロピルメチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、澱粉、ポリエチレンオキシド、ポリアクリル酸ソーダ、ポリアクリルアミド、ポリビニルアセトアミド、ポリビニルホルムアミド等の親水性の樹脂が挙げられる。該チタン塩水溶液に、該水溶性高分子を含有させることにより、酸化チタン粒子の結晶構造又は結晶状態を変化させることができる。 The aqueous titanium salt solution can contain a water-soluble polymer together with the alkali metal halide. Examples of the water-soluble polymer include hydrophilic properties such as polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, hydroxylpropyl methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, starch, polyethylene oxide, sodium polyacrylate, polyacrylamide, polyvinyl acetamide, and polyvinyl formamide. These resins are mentioned. By containing the water-soluble polymer in the titanium salt aqueous solution, the crystal structure or crystal state of the titanium oxide particles can be changed.
該チタン塩水溶液中、該チタン塩の濃度は、０．１〜０．３モル／リットル、好ましくは０．１４〜０．１６モル／リットルである。該チタン塩水溶液中の該チタン塩の濃度が上記範囲内にあることにより、酸化チタン粒子の光触媒活性が高くなる。 The concentration of the titanium salt in the aqueous titanium salt solution is 0.1 to 0.3 mol / liter, preferably 0.14 to 0.16 mol / liter. When the concentration of the titanium salt in the aqueous titanium salt solution is within the above range, the photocatalytic activity of the titanium oxide particles is increased.
該チタン塩水溶液中、該アルカリ金属のハロゲン化物の濃度は、１〜５モル／リットル、好ましくは２．５〜３．５モル／リットルである。該チタン塩水溶液中の該アルカリ金属のハロゲン化物の濃度が、上記範囲内であることにより、酸化チタン粒子の光触媒活性が高くなる。 The concentration of the alkali metal halide in the aqueous titanium salt solution is 1 to 5 mol / liter, preferably 2.5 to 3.5 mol / liter. When the concentration of the alkali metal halide in the aqueous titanium salt solution is within the above range, the photocatalytic activity of the titanium oxide particles is increased.
該チタン塩水溶液中、該チタン塩に対する該アルカリ金属のハロゲン化物のモル比（アルカリ金属のハロゲン化物／チタン塩）は、好ましくは３〜５０、特に好ましくは１５〜２５である。該チタン塩水溶液中、該チタン塩に対する該アルカリ金属のハロゲン化物のモル比が上記範囲内にあることにより、酸化チタン粒子の光触媒活性が高くなる。 In the aqueous titanium salt solution, the molar ratio of the alkali metal halide to the titanium salt (alkali metal halide / titanium salt) is preferably 3 to 50, particularly preferably 15 to 25. When the molar ratio of the alkali metal halide to the titanium salt in the titanium salt aqueous solution is within the above range, the photocatalytic activity of the titanium oxide particles is increased.
そして、本発明の酸化チタンの製造方法では、該アルカリ金属のハロゲン化物を含有するチタン塩水溶液を、水熱処理することにより、酸化チタン粒子を生成させ、酸化チタン粒子を得る。該水熱処理は、先ず、該アルカリ金属のハロゲン化物を含有するチタン塩水溶液を調製し、次いで、密閉容器中に、該アルカリ金属のハロゲン化物を含有するチタン塩水溶液を入れ、密閉し、１２０〜２００℃で加熱して、水熱処理を行う。該水熱処理の際の圧力は、温度により変化する。また、該水熱処理の時間は、反応条件により適宜選択され、通常、３〜２４時間である。 And in the manufacturing method of the titanium oxide of this invention, titanium oxide particle is produced | generated by carrying out the hydrothermal treatment of the titanium salt aqueous solution containing the halide of this alkali metal, and obtaining a titanium oxide particle. In the hydrothermal treatment, first, an aqueous solution of a titanium salt containing the alkali metal halide is prepared, and then the aqueous solution of the titanium salt containing the alkali metal halide is placed in a sealed container and sealed, Hydrothermal treatment is performed by heating at 200 ° C. The pressure during the hydrothermal treatment varies depending on the temperature. Moreover, the time of this hydrothermal treatment is suitably selected according to reaction conditions, and is normally 3 to 24 hours.
以下に、本発明の酸化チタン粒子の製造方法のうち、該チタン塩水溶液として三塩化チタンを用い、該アルカリ金属のハロゲン化物として塩化ナトリウムを用いる形態例（以下、該チタン塩水溶液として三塩化チタンを用い、該アルカリ金属のハロゲン化物として塩化ナトリウムを用いる形態例を、本発明の酸化チタン粒子の製造方法（１）とも記載する。）について、説明する。 Hereinafter, in the method for producing titanium oxide particles of the present invention, an embodiment using titanium trichloride as the titanium salt aqueous solution and sodium chloride as the alkali metal halide (hereinafter referred to as titanium trichloride as the titanium salt aqueous solution). An embodiment in which sodium chloride is used as the alkali metal halide is also described as a method (1) for producing titanium oxide particles of the present invention.)
本発明の酸化チタン粒子の製造方法（１）では、先ず、塩化ナトリウムを含有する三塩化チタン水溶液を得る。次いで、密閉容器中に、塩化ナトリウムを含有する三塩化チタン水溶液を入れ、密閉し、１２０〜２００℃で加熱して、水熱処理を行う。該水熱処理の際の圧力は、温度により変化する。また、該水熱処理の時間は、反応条件により適宜選択され、通常、３〜２４時間である。 In the method (1) for producing titanium oxide particles of the present invention, first, a titanium trichloride aqueous solution containing sodium chloride is obtained. Next, a titanium trichloride aqueous solution containing sodium chloride is placed in a sealed container, sealed, and heated at 120 to 200 ° C. to perform hydrothermal treatment. The pressure during the hydrothermal treatment varies depending on the temperature. Moreover, the time of this hydrothermal treatment is suitably selected according to reaction conditions, and is normally 3 to 24 hours.
該三塩化チタン水溶液中、三塩化チタンの濃度は、０．１〜０．３モル／リットル、好ましくは０．１４〜０．１６モル／リットルである。該三塩化チタン水溶液中の三塩化チタンの濃度が、上記範囲内であることにより、結晶相がルチル型単相の柱状の酸化チタン粒子が得られる。 The concentration of titanium trichloride in the aqueous titanium trichloride solution is 0.1 to 0.3 mol / liter, preferably 0.14 to 0.16 mol / liter. When the concentration of titanium trichloride in the aqueous titanium trichloride solution is within the above range, columnar titanium oxide particles having a rutile type single crystal phase can be obtained.
該三塩化チタン水溶液中、塩化ナトリウムの濃度は、１〜５モル／リットル、好ましくは２．５〜３．５モル／リットルである。該三塩化チタン水溶液中の塩化ナトリウムの濃度が、上記範囲内であることにより、ルチル型単相で光触媒活性が高い酸化チタン粒子が得られる。 The concentration of sodium chloride in the aqueous titanium trichloride solution is 1 to 5 mol / liter, preferably 2.5 to 3.5 mol / liter. When the concentration of sodium chloride in the aqueous titanium trichloride solution is within the above range, titanium oxide particles having a rutile single phase and high photocatalytic activity can be obtained.
該三塩化チタン水溶液中、三塩化チタンに対する塩化ナトリウムのモル比（塩化ナトリウム／三塩化チタン）は、好ましくは３〜５０、特に好ましくは６〜３５、更に好ましくは１５〜２５である。三塩化チタンに対する塩化ナトリウムのモル比が上記範囲内にあることにより、ルチル型単相で光触媒活性が高い酸化チタン粒子が得られる。 In the titanium trichloride aqueous solution, the molar ratio of sodium chloride to titanium trichloride (sodium chloride / titanium trichloride) is preferably 3 to 50, particularly preferably 6 to 35, and further preferably 15 to 25. When the molar ratio of sodium chloride to titanium trichloride is within the above range, titanium oxide particles having a rutile single phase and high photocatalytic activity can be obtained.
そして、該三塩化チタン水溶液中の三塩化チタンの濃度を、０．１〜０．１５モル／リットルとすることにより、酸化チタン粒子の光触媒活性を更に高めることができる。また、該水熱処理の時間を、１２時間以内にすることにより、酸化チタン粒子の光触媒活性を更に高めることができる。 And the photocatalytic activity of a titanium oxide particle can be further improved by making the density | concentration of the titanium trichloride in this titanium trichloride aqueous solution into 0.1-0.15 mol / liter. Moreover, the photocatalytic activity of the titanium oxide particles can be further enhanced by setting the hydrothermal treatment time to 12 hours or less.
本発明の酸化チタンの製造方法（１）を行い得られる酸化チタン粒子は、光触媒用酸化チタン粒子として、好適に用いられる。該酸化チタンは、結晶相がルチル型であり、形状は柱状である。該酸化チタン粒子の構造の一例を図１に示す。該酸化チタン粒子の形状は柱状であり、該酸化チタン粒子には平滑な結晶面が露出しており、柱状粒子の側面は（１１０）面であり、先端面は（１１１）面である。 The titanium oxide particles obtained by carrying out the titanium oxide production method (1) of the present invention are suitably used as photocatalyst titanium oxide particles. The titanium oxide has a rutile type crystal phase and a columnar shape. An example of the structure of the titanium oxide particles is shown in FIG. The shape of the titanium oxide particles is columnar, and a smooth crystal plane is exposed on the titanium oxide particles, the side surfaces of the columnar particles are the (110) plane, and the tip surface is the (111) plane.
本発明の酸化チタンの製造方法（１）では、三塩化チタン水溶液中の塩化ナトリウムの濃度により、ミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）が、変化する。なお、このＸ線回折強度とは、ローレンツ関数を用いてパターンフィッティングを行うことにより得られたピーク面積強度の値である。 In the titanium oxide production method (1) of the present invention, the X-ray diffraction intensity ratio ((002) plane / (002) plane / (110) plane in the Miller index display) depends on the concentration of sodium chloride in the aqueous titanium trichloride solution. (110) plane) changes. The X-ray diffraction intensity is a peak area intensity value obtained by performing pattern fitting using a Lorentz function.
そして、該三塩化チタン水溶液中の三塩化チタンの濃度を、０．１〜０．３モル／リットル、好ましくは０．１４〜０．１６モル／リットルとし、該三塩化チタン水溶液中の塩化ナトリウムの濃度を、１〜５モル／リットル、好ましくは２．５〜３．５モル／リットルとすることにより、酸化チタン粒子を、ルチル型単相であり且つミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）を、０．２９〜１．３に制御し易くなり、このことにより、酸化チタン粒子の光触媒活性が高くなる。 The concentration of titanium trichloride in the titanium trichloride aqueous solution is 0.1 to 0.3 mol / liter, preferably 0.14 to 0.16 mol / liter, and sodium chloride in the titanium trichloride aqueous solution is used. Is set to 1 to 5 mol / liter, preferably 2.5 to 3.5 mol / liter, so that the titanium oxide particles have a rutile type single phase and (110) plane in the Miller index display ( The X-ray diffraction intensity ratio of the (002) plane ((002) plane / (110) plane) can be easily controlled to 0.29 to 1.3, which increases the photocatalytic activity of the titanium oxide particles.
更に、本発明の酸化チタン粒子の製造方法（１）では、該三塩化チタン水溶液中の三塩化チタンに対する塩化ナトリウムのモル比（塩化ナトリウム／三塩化チタン）を、好ましくは３〜５０、特に好ましくは６〜３５、更に好ましくは１５〜２５とすることにより、酸化チタン粒子を、ルチル型単相であり且つミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）を、０．２９〜１．３に制御し易くなる。 Furthermore, in the method (1) for producing titanium oxide particles of the present invention, the molar ratio of sodium chloride to titanium trichloride (sodium chloride / titanium trichloride) in the titanium trichloride aqueous solution is preferably 3 to 50, particularly preferably. Is 6 to 35, more preferably 15 to 25, so that the titanium oxide particles are in a rutile type single phase and have an X-ray diffraction intensity ratio ((002) of (002) plane to (110) plane in Miller index display. ) Plane / (110) plane) is easily controlled to 0.29 to 1.3.
本発明の酸化チタン粒子は、光触媒用酸化チタン粒子である。本発明の酸化チタン粒子は、ミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）は、０．２９〜１．３である。該酸化チタンのミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）が、上記範囲内にあることにより、酸化チタン粒子の光触媒活性が高くなる。 The titanium oxide particles of the present invention are titanium oxide particles for photocatalyst. In the titanium oxide particles of the present invention, the X-ray diffraction intensity ratio ((002) plane / (110) plane) of the (002) plane to the (110) plane in the Miller index display is 0.29 to 1.3. When the X-ray diffraction intensity ratio of the (002) plane to the (110) plane ((002) plane / (110) plane) in the mirror index display of the titanium oxide is within the above range, the photocatalytic activity of the titanium oxide particles Becomes higher.
本発明の酸化チタン粒子は、好ましくは結晶相がルチル型であり且つ形状が柱状である。結晶相がルチル型であり且つ形状が柱状であることにより、酸化チタン粒子の光触媒活性が高くなる。 The titanium oxide particles of the present invention preferably have a rutile type crystal phase and a columnar shape. When the crystal phase is a rutile type and the shape is columnar, the photocatalytic activity of the titanium oxide particles is increased.
次に、実施例を挙げて本発明を更に具体的に説明するが、これは単に例示であって、本発明を制限するものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.
（光触媒活性の評価）
評価対象の酸化チタン１００ｍｇを、シャーレに均一に広げ、１２５ミリリットルのテドラバック内に封入した。真空排気後、アセトアルデヒドが５００ｐｐｍとなるように、アセトアルデヒドと空気の混合気体をテドラバック内に注入した。吸着平衡に達した後、光照射を開始し、二酸化炭素生成量を、水素炎イオン化検出器を備えたガスクロマトグラフ（ＧＣ−ＦＩＤ）により測定した。なお、照射光源には、５００Ｗキセノンランプを用い、色ガラスフィルタＵＶ−３５（株式会社ケンコー製）を取り付け、約３５０ｎｍ以上の光（３０ｍＷ／ｃｍ２）を試料に照射した。
(Evaluation of photocatalytic activity)
100 mg of titanium oxide to be evaluated was spread evenly on a petri dish and sealed in a 125 ml tedra bag. After evacuation, a mixed gas of acetaldehyde and air was injected into the tedra bag so that the acetaldehyde was 500 ppm. After reaching adsorption equilibrium, light irradiation was started, and the amount of carbon dioxide produced was measured by a gas chromatograph (GC-FID) equipped with a flame ionization detector. A 500 W xenon lamp was used as the irradiation light source, a colored glass filter UV-35 (manufactured by Kenko Co., Ltd.) was attached, and the sample was irradiated with light of about 350 nm or more (30 mW / cm 2 ).
（Ｘ線回折分析）
以下のＸ線回折測定条件にて行った。
回折装置 ＪＤＸ３５００Ｋ（日本電子株式会社製）
Ｘ線管球 Ｃｕ
管電圧・管電流 ４０ｋＶ、３００ｍＡ
スリット 発散：１°、受光：０．２ｍｍ、散乱：１°
モノクロメータ グラファイト
測定間隔 ０．０５０°
計数方法 定時計数測定
Ｘ線回折強度は、得られた回折チャートより、ローレンツ関数を用いたパターンフィッティングにより得られたピーク面積強度から求めた。
(X-ray diffraction analysis)
The measurement was performed under the following X-ray diffraction measurement conditions.
Diffraction device JDX3500K (manufactured by JEOL Ltd.)
X-ray tube Cu
Tube voltage / tube current 40kV, 300mA
Slit Divergence: 1 °, Light reception: 0.2mm, Scattering: 1 °
Monochromator Graphite Measurement interval 0.050 °
Counting Method Constant Clock Count Measurement X-ray diffraction intensity was determined from the peak area intensity obtained by pattern fitting using a Lorentz function from the obtained diffraction chart.
（実施例１）＜塩化ナトリウム濃度＝１モル／リットル＞
チタン濃度が３．５モル／リットルの三塩化チタン水溶液（約２０％希塩酸溶液）を用い、塩化ナトリウムと、蒸留水を加え、三塩化チタン濃度が０．１５モル／リットル、塩化ナトリウムの濃度が１モル／リットルの塩化ナトリウム含有三塩化チタン水溶液を調製した。三塩化チタンに対する塩化ナトリウムのモル比（塩化ナトリウム／三塩化チタン）は、６．７である。
次いで、この水溶液５０ミリリットルを、テフロン（登録商標）容器に入れ、耐圧ステンレス製外筒を装着後、２００℃、３時間で、水熱処理を行い、酸化チタン粒子を得た。
得られた酸化チタン粒子を、Ｘ線粉末回折測定により分析したところ、得られた酸化チタン粒子は、ルチル型単相であった。また、ミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）は０．２９であった。
また、得られた酸化チタン粒子を、透過型電子顕微鏡により分析した。その結果を、図１に示すが、形状は柱状であり、長さは１００〜３００ｎｍ、幅は２０〜１００ｎｍであった。また、該酸化チタンには、平滑な結晶面が露出しており、柱状粒子の側面は（１１０）面であり、先端面は（１１１）面であった。
従って、酸化チタン粒子表面の結晶面の還元力の差を利用して、特定の結晶面に白金等の貴金属を担持することが可能である。
得られた酸化チタン粒子の光触媒活性を測定した。その結果を表１及び図２に示す。
(Example 1) <Sodium chloride concentration = 1 mol / liter>
Using a titanium trichloride aqueous solution (approximately 20% dilute hydrochloric acid solution) with a titanium concentration of 3.5 mol / liter, sodium chloride and distilled water were added, the titanium trichloride concentration was 0.15 mol / liter, and the sodium chloride concentration was A 1 mol / liter sodium chloride-containing titanium trichloride aqueous solution was prepared. The molar ratio of sodium chloride to titanium trichloride (sodium chloride / titanium trichloride) is 6.7.
Next, 50 ml of this aqueous solution was put into a Teflon (registered trademark) container, and after mounting a pressure resistant stainless steel outer tube, hydrothermal treatment was performed at 200 ° C. for 3 hours to obtain titanium oxide particles.
When the obtained titanium oxide particles were analyzed by X-ray powder diffraction measurement, the obtained titanium oxide particles were in a rutile type single phase. The X-ray diffraction intensity ratio of the (002) plane to the (110) plane ((002) plane / (110) plane) in the Miller index display was 0.29.
The obtained titanium oxide particles were analyzed with a transmission electron microscope. The result is shown in FIG. 1, and the shape was columnar, the length was 100 to 300 nm, and the width was 20 to 100 nm. Further, the titanium oxide had a smooth crystal face exposed, the side surfaces of the columnar particles were (110) faces, and the tip face was (111) faces.
Therefore, it is possible to carry a noble metal such as platinum on a specific crystal plane by utilizing the difference in reducing power of the crystal plane on the titanium oxide particle surface.
The photocatalytic activity of the obtained titanium oxide particles was measured. The results are shown in Table 1 and FIG.
（実施例２）＜塩化ナトリウム濃度＝３モル／リットル＞
塩化ナトリウムの濃度を、３モル／リットルとする以外は、実施例１と同様の方法で、水熱処理を行い、酸化チタン粒子を得た。三塩化チタンに対する塩化ナトリウムのモル比（塩化ナトリウム／三塩化チタン）は、２０である。
得られた酸化チタン粒子を、Ｘ線粉末回折測定により分析したところ、得られた酸化チタン粒子は、ルチル型単相であった。また、ミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）は０．５８であった。
また、得られた酸化チタン粒子を、透過型電子顕微鏡により分析した。その結果を、図３に示すが、形状は柱状であり、長さは１００〜３００ｎｍ、幅は２０〜１００ｎｍであった。また、該酸化チタンには、平滑な結晶面が露出しており、柱状粒子の側面は（２００）面、そしてこの面より４５°傾いた（１１０）面であり、先端面は（１１１）面と（００１）面であった。
従って、酸化チタン粒子表面の結晶面の還元力の差を利用して、特定の結晶面に白金等の貴金属を担持することが可能である。
得られた酸化チタン粒子の光触媒活性を測定した。その結果を表１及び図２に示す。
(Example 2) <Sodium chloride concentration = 3 mol / liter>
Except that the concentration of sodium chloride was 3 mol / liter, hydrothermal treatment was performed in the same manner as in Example 1 to obtain titanium oxide particles. The molar ratio of sodium chloride to titanium trichloride (sodium chloride / titanium trichloride) is 20.
When the obtained titanium oxide particles were analyzed by X-ray powder diffraction measurement, the obtained titanium oxide particles were in a rutile type single phase. The X-ray diffraction intensity ratio ((002) plane / (110) plane) of the (002) plane with respect to the (110) plane in the Miller index display was 0.58.
The obtained titanium oxide particles were analyzed with a transmission electron microscope. The results are shown in FIG. 3, and the shape was columnar, the length was 100 to 300 nm, and the width was 20 to 100 nm. Further, the titanium oxide has a smooth crystal face exposed, the side surfaces of the columnar particles are the (200) plane, the (110) plane inclined by 45 ° from this plane, and the tip end face is the (111) plane. And (001) plane.
Therefore, it is possible to support a noble metal such as platinum on a specific crystal plane by utilizing the difference in reducing power of the crystal plane on the titanium oxide particle surface.
The photocatalytic activity of the obtained titanium oxide particles was measured. The results are shown in Table 1 and FIG.
（実施例３）＜塩化ナトリウム濃度＝５モル／リットル＞
塩化ナトリウムの濃度を、５モル／リットルとする以外は、実施例１と同様の方法で、水熱処理を行い、酸化チタン粒子を得た。三塩化チタンに対する塩化ナトリウムのモル比（塩化ナトリウム／三塩化チタン）は、３３である。
得られた酸化チタン粒子を、Ｘ線粉末回折測定により分析したところ、得られた酸化チタン粒子は、ルチル型単相であった。また、ミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）は１．３であった。
また、得られた酸化チタン粒子を、透過型電子顕微鏡により分析した。その結果を、図４に示すが、形状は柱状であり、長さは１００〜３００ｎｍ、幅は２０〜１００ｎｍであった。また、該酸化チタンには、平滑な結晶面が露出しており、柱状粒子の側面は（１１０）面であり、先端面は（０１１）面であった。
従って、酸化チタン粒子表面の結晶面の還元力の差を利用して、特定の結晶面に白金等の貴金属を担持することが可能である。
得られた酸化チタン粒子の光触媒活性を測定した。その結果を表１及び図２に示す。
(Example 3) <Sodium chloride concentration = 5 mol / liter>
Except that the concentration of sodium chloride was 5 mol / liter, hydrothermal treatment was performed in the same manner as in Example 1 to obtain titanium oxide particles. The molar ratio of sodium chloride to titanium trichloride (sodium chloride / titanium trichloride) is 33.
When the obtained titanium oxide particles were analyzed by X-ray powder diffraction measurement, the obtained titanium oxide particles were in a rutile type single phase. The X-ray diffraction intensity ratio ((002) plane / (110) plane) of the (002) plane with respect to the (110) plane in the Miller index display was 1.3.
The obtained titanium oxide particles were analyzed with a transmission electron microscope. The result is shown in FIG. 4, and the shape was columnar, the length was 100 to 300 nm, and the width was 20 to 100 nm. Further, the titanium oxide had a smooth crystal plane exposed, the side surfaces of the columnar particles were the (110) plane, and the tip surface was the (011) plane.
Therefore, it is possible to carry a noble metal such as platinum on a specific crystal plane by utilizing the difference in reducing power of the crystal plane on the titanium oxide particle surface.
The photocatalytic activity of the obtained titanium oxide particles was measured. The results are shown in Table 1 and FIG.
（比較例１）＜ＭＴ−６００Ｂ＞
市販の酸化チタン（ＭＴ−６００Ｂ、テイカ株式会社製）を、Ｘ線粉末回折測定により分析したところ、該酸化チタン粒子は、ルチル型単相であった。また、ミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）は０．１２であった。
また、該酸化チタン粒子を、透過型電子顕微鏡により分析した。その結果を、図５に示すが、形状は球形であり、大きさは５０〜３００ｎｍであった。また、該酸化チタンの表面には、平滑な結晶面は見られなかった。
該酸化チタン粒子の光触媒活性を測定した。その結果を表１及び図２に示す。
(Comparative Example 1) <MT-600B>
When commercially available titanium oxide (MT-600B, manufactured by Teika Co., Ltd.) was analyzed by X-ray powder diffraction measurement, the titanium oxide particles were a rutile type single phase. Further, the X-ray diffraction intensity ratio of the (002) plane to the (110) plane ((002) plane / (110) plane) in the Miller index display was 0.12.
The titanium oxide particles were analyzed with a transmission electron microscope. The result is shown in FIG. 5, and the shape was spherical and the size was 50 to 300 nm. Further, no smooth crystal plane was observed on the surface of the titanium oxide.
The photocatalytic activity of the titanium oxide particles was measured. The results are shown in Table 1 and FIG.
（比較例２）＜塩化ナトリウム濃度＝０モル／リットル＞
塩化ナトリウムの濃度を、０モル/リットル、すなわち、塩化ナトリウムを加えない以外は、実施例１と同様の方法で、水熱処理を行い、酸化チタン粒子を得た。
得られた酸化チタン粒子を、Ｘ線粉末回折測定により分析したところ、得られた酸化チタン粒子は、ルチル型及びブルッカイト型の混相（ルチル型：ブルッカイト型＝２：１）であった。また、ミラー指数表示における（１１０）面に対する（００２）面のＸ線回折強度比（（００２）面／（１１０）面）は０．１５であった。
また、得られた酸化チタン粒子を、透過型電子顕微鏡により分析した。その結果を、図６に示すが、形状は、長さが２００〜５００ｎｍ、幅が１０〜１００ｎｍの柱状粒子と、２０ｎｍ程度の大きさのアスペクト比が１に近い立方体状の粒子であった。また、該酸化チタンには、平滑な結晶面が露出していた。
(Comparative Example 2) <Sodium chloride concentration = 0 mol / liter>
The concentration of sodium chloride was 0 mol / liter, that is, hydrothermal treatment was performed in the same manner as in Example 1 except that sodium chloride was not added to obtain titanium oxide particles.
When the obtained titanium oxide particles were analyzed by X-ray powder diffraction measurement, the obtained titanium oxide particles were a mixed phase of rutile type and brookite type (rutile type: brookite type = 2: 1). The X-ray diffraction intensity ratio ((002) plane / (110) plane) of the (002) plane with respect to the (110) plane in the Miller index display was 0.15.
The obtained titanium oxide particles were analyzed with a transmission electron microscope. The results are shown in FIG. 6, and the shapes were columnar particles having a length of 200 to 500 nm and a width of 10 to 100 nm, and cubic particles having an aspect ratio of about 20 nm and an aspect ratio close to 1. The titanium oxide had a smooth crystal face exposed.
本発明によれば、光触媒活性が高い酸化チタン粒子を製造することができる。 According to the present invention, titanium oxide particles having high photocatalytic activity can be produced.
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