JP2011001238A - Method for producing brookite-type titanium dioxide nanoparticle - Google Patents
Method for producing brookite-type titanium dioxide nanoparticle Download PDFInfo
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- JP2011001238A JP2011001238A JP2009147142A JP2009147142A JP2011001238A JP 2011001238 A JP2011001238 A JP 2011001238A JP 2009147142 A JP2009147142 A JP 2009147142A JP 2009147142 A JP2009147142 A JP 2009147142A JP 2011001238 A JP2011001238 A JP 2011001238A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 54
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002071 nanotube Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
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- 150000001875 compounds Chemical class 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 229920002620 polyvinyl fluoride Polymers 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 1
- FOWDOWQYRZXQDP-UHFFFAOYSA-N adamantan-2-ol Chemical compound C1C(C2)CC3CC1C(O)C2C3 FOWDOWQYRZXQDP-UHFFFAOYSA-N 0.000 description 1
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、光触媒、酸化触媒、光電池材料、誘電体材料等として有用なブルッカイト型二酸化チタンナノ粒子の製造法、該製造法により得られるブルッカイト型二酸化チタンナノ粒子、及び該ブルッカイト型二酸化チタンナノ粒子を用いた有機化合物の酸化方法に関する。 The present invention uses a method for producing brookite-type titanium dioxide nanoparticles useful as a photocatalyst, an oxidation catalyst, a photovoltaic cell material, a dielectric material, etc., brookite-type titanium dioxide nanoparticles obtained by the production method, and the brookite-type titanium dioxide nanoparticles. The present invention relates to a method for oxidizing an organic compound.
二酸化チタンには、アナターゼ型、ルチル型、ブルッカイト型の３種の結晶形態が存在する。そのうち、ブルッカイト型二酸化チタンの製造法としては、水酸化ナトリウム水溶液に非晶質二酸化チタンを特定量添加し、特定の温度で水熱処理する方法（特許文献１参照）、三塩化チタンと尿素の混合液を加熱して水酸化チタンを得、これを酸化性雰囲気中で乾燥させる方法（特許文献２参照）、原料チタン化合物をペルオキソ化した後、水熱処理する方法（特許文献３参照）、ヒドロキシカルボン酸チタン錯体を含む水溶液を特定のｐＨの範囲で水熱処理する方法などが知られている（特許文献４参照）。 Titanium dioxide has three types of crystal forms, anatase type, rutile type, and brookite type. Among them, as a method for producing brookite-type titanium dioxide, a specific amount of amorphous titanium dioxide is added to an aqueous sodium hydroxide solution and hydrothermally treated at a specific temperature (see Patent Document 1), and a mixture of titanium trichloride and urea. A method of heating the liquid to obtain titanium hydroxide and drying it in an oxidizing atmosphere (see Patent Document 2), a method of peroxylating the raw material titanium compound and hydrothermally treating it (see Patent Document 3), hydroxycarbon A method of hydrothermally treating an aqueous solution containing an acid titanium complex in a specific pH range is known (see Patent Document 4).
しかしながら、これらの方法は、原料の入手容易性、操作性、生成物の純度等の点で必ずしも十分満足できるものではなかった。 However, these methods are not always satisfactory in terms of availability of raw materials, operability, product purity, and the like.
従って、本発明の目的は、入手しやすい原料から簡易な手段で高純度のブルッカイト型二酸化チタンナノ粒子を効率よく製造できる方法を提供することにある。 Accordingly, an object of the present invention is to provide a method capable of efficiently producing high-purity brookite-type titanium dioxide nanoparticles from readily available raw materials by a simple means.
本発明者らは、上記目的を達成するため鋭意検討した結果、チタネートナノチューブを強酸の存在下で水熱処理すると、簡易な操作で、純度の高いブルッカイト型二酸化チタンナノ粒子を効率よく製造できることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that titanate nanotubes can be efficiently produced with high purity brookite-type titanium dioxide nanoparticles by a simple operation when hydrothermally treated in the presence of a strong acid, The present invention has been completed.
すなわち、本発明は、チタネートナノチューブを強酸の存在下で水熱処理する工程を含むブルッカイト型二酸化チタンナノ粒子の製造法を提供する。 That is, the present invention provides a method for producing brookite-type titanium dioxide nanoparticles including a step of hydrothermally treating titanate nanotubes in the presence of a strong acid.
この製造法において、水熱処理後、生成した二酸化チタン粒子を水に分散させ、遠心分離により精製する工程を含むのが好ましい。 In this production method, it is preferable to include a step of dispersing the produced titanium dioxide particles in water after the hydrothermal treatment and purifying by centrifugation.
本発明は、また、前記の製造法により得られるブルッカイト型二酸化チタンナノ粒子を提供する。 The present invention also provides brookite-type titanium dioxide nanoparticles obtained by the production method described above.
本発明は、さらに、前記のブルッカイト型二酸化チタンナノ粒子の存在下、有機化合物を酸化することを特徴とする有機化合物の酸化方法を提供する。 The present invention further provides an organic compound oxidation method characterized by oxidizing an organic compound in the presence of the brookite-type titanium dioxide nanoparticles.
本発明によれば、入手容易な原料から、簡易な手段で、純度の高いブルッカイト型二酸化チタンナノ粒子を効率よく製造できる。 According to the present invention, high-purity brookite-type titanium dioxide nanoparticles can be efficiently produced from readily available raw materials by a simple means.
本発明のブルッカイト型二酸化チタンナノ粒子の製造法は、チタネートナノチューブを強酸の存在下で水熱処理する工程を含む。 The method for producing brookite-type titanium dioxide nanoparticles of the present invention includes a step of hydrothermally treating titanate nanotubes in the presence of a strong acid.
原料として用いられるチタネートナノチューブは公知の方法により調製できる。また、市販のチタネートナノチューブを用いることもできる。チタネートナノチューブの比表面積としては、例えば、１００〜１０００ｍ2／ｇ、好ましくは１５０〜４００ｍ2／ｇ程度である。 The titanate nanotube used as a raw material can be prepared by a known method. Commercially available titanate nanotubes can also be used. The specific surface area of titanate nanotubes, for example, 100~1000m 2 / g, preferably from 150 to 400 m 2 / g approximately.
水熱処理は、強酸の水溶液中で行われる。前記強酸としては、例えば、硫酸、硝酸、塩化水素、過塩素酸などの無機酸が挙げられる。これらの中でも、硝酸、過塩素酸が好ましく、特に過塩素酸が好ましい。 Hydrothermal treatment is performed in an aqueous solution of a strong acid. Examples of the strong acid include inorganic acids such as sulfuric acid, nitric acid, hydrogen chloride, and perchloric acid. Among these, nitric acid and perchloric acid are preferable, and perchloric acid is particularly preferable.
水熱処理時の強酸の濃度は、好ましくは０．１ｍｏｌ／Ｌ以上、さらに好ましくは０．５ｍｏｌ／Ｌ以上である。強酸の濃度の上限は特に限定されないが、取扱性等の点から、一般には１０ｍｏｌ／Ｌ程度以下である。強酸の濃度が低すぎると、生成する二酸化チタン結晶において、アナターゼ相の割合が多く、ブルッカイト相の割合は低くなる。 The concentration of the strong acid during the hydrothermal treatment is preferably 0.1 mol / L or more, more preferably 0.5 mol / L or more. The upper limit of the strong acid concentration is not particularly limited, but is generally about 10 mol / L or less from the viewpoint of handleability. If the concentration of the strong acid is too low, the proportion of anatase phase is large and the proportion of brookite phase is low in the produced titanium dioxide crystal.
水熱処理の温度は、例えば１００〜２５０℃程度、好ましくは１５０〜２２０℃である。 The temperature of the hydrothermal treatment is, for example, about 100 to 250 ° C, preferably 150 to 220 ° C.
チタネートナノチューブに水熱処理を施すと、最初はアナターゼ相の結晶が主であるが、水熱時間を延ばすことにより、アナターゼ相は消失し、ブルッカイト相とルチル相が生成する。各結晶相の比率は、ＸＲＤ分析により公知の手法で求めることができる（例えば、J. Phys. Chem. B 104(2000)3481 参照）。 When a titanate nanotube is subjected to a hydrothermal treatment, initially anatase phase crystals are predominant, but by extending the hydrothermal time, the anatase phase disappears, and a brookite phase and a rutile phase are generated. The ratio of each crystal phase can be determined by a known method by XRD analysis (see, for example, J. Phys. Chem. B 104 (2000) 3481).
なお、酸の種類の違いにより、生成する相の傾向が異なる。例えば、酸として過塩素酸を用いた場合には、水熱処理の時間の経過と共に、アナターゼ相は消失し、ブルッカイト相が優先して生成する。ルチル相の生成量はわずかである。従って、酸として過塩素酸を用いた場合には、水熱処理時間は、好ましくは２時間以上（例えば、２〜１００時間）、好ましくは２０〜６０時間である。 In addition, the tendency of the produced | generated phase changes with the difference in the kind of acid. For example, when perchloric acid is used as the acid, the anatase phase disappears with the passage of time of the hydrothermal treatment, and the brookite phase is preferentially generated. The amount of rutile phase produced is small. Accordingly, when perchloric acid is used as the acid, the hydrothermal treatment time is preferably 2 hours or longer (for example, 2 to 100 hours), preferably 20 to 60 hours.
また、酸として塩化水素を用いた場合には、水熱処理の時間の経過と共に、アナターゼ相は消失し、ブルッカイト相とルチル相が生成するが、一旦生成したブルッカイト相も次第に少なくなり、ルチル相が主生成物となる。従って、酸として塩化水素を用いた場合の水熱処理時間は、好ましくは０．５〜２時間程度である。 When hydrogen chloride is used as the acid, the anatase phase disappears with the passage of time of the hydrothermal treatment, and a brookite phase and a rutile phase are produced. However, once the brookite phase is produced, the rutile phase is gradually reduced. The main product. Accordingly, the hydrothermal treatment time when hydrogen chloride is used as the acid is preferably about 0.5 to 2 hours.
酸として硝酸を用いた場合には、水熱処理の時間の経過と共に、アナターゼ相は消失し、ブルッカイト相とルチル相が生成するが、一旦生成したブルッカイト相も次第に少なくなり、ルチル相とブルッカイト相がほぼ同量の混合物となる。従って、酸として硝酸を用いた場合の水熱処理時間は、好ましくは０．５〜２０時間程度である。 When nitric acid is used as the acid, the anatase phase disappears with the passage of time of the hydrothermal treatment, and a brookite phase and a rutile phase are produced, but once the brookite phase is produced, the rutile phase and the brookite phase are gradually reduced. The mixture is almost the same amount. Therefore, the hydrothermal treatment time when nitric acid is used as the acid is preferably about 0.5 to 20 hours.
水熱処理後、遠心分離等により生成した二酸化チタン粒子を取得できる。この二酸化チタン粒子を精製することにより、ブルッカイト型二酸化チタンナノ粒子を得ることができる。精製法としては特に限定されないが、上記二酸化チタン粒子を水（好ましくは、イオン交換水）に分散させ、遠心分離により精製する方法が好ましい。 After hydrothermal treatment, titanium dioxide particles produced by centrifugation or the like can be obtained. By purifying the titanium dioxide particles, brookite-type titanium dioxide nanoparticles can be obtained. Although it does not specifically limit as a purification method, The method of disperse | distributing the said titanium dioxide particle to water (preferably ion-exchange water), and refine | purifying by centrifugation is preferable.
この遠心分離は、例えば、１０００〜１００００ｒｐｍ程度の回転数で、１０〜６０分程度行う。遠心分離後、上澄み（不透明）を濾過し、濾物（濾さい）を、例えばアンモニア水で洗浄し、さらにイオン交換水で伝導度が例えば１０μＳ／ｃｍ2以下になるまで洗浄し、真空乾燥することにより、高純度のブルッカイト型二酸化チタンナノ粒子を得ることができる。得られるブルッカイト型二酸化チタンナノ粒子は立方体構造を有しており、粒径は２０ｎｍ程度で、粒の大きさは揃っている。 This centrifugation is performed for about 10 to 60 minutes at a rotational speed of about 1000 to 10000 rpm, for example. After centrifugation, the supernatant (opaque) is filtered, and the filtrate (filter) is washed with, for example, ammonia water, and further washed with ion-exchanged water until the conductivity becomes, for example, 10 μS / cm 2 or less, followed by vacuum drying. As a result, high-purity brookite-type titanium dioxide nanoparticles can be obtained. The resulting brookite-type titanium dioxide nanoparticles have a cubic structure, a particle size of about 20 nm, and a uniform size.
こうして得られるブルッカイト型二酸化チタンナノ粒子は、種々の化学反応（例えば、酸化反応、有害物質の分解反応等）や殺菌などの従来の酸化チタン光触媒と同様の分野で利用することができる。また、上記ブルッカイト型二酸化チタンナノ粒子の表面に金属又は金属化合物（金属イオン等）を担持した表面修飾ブルッカイト型二酸化チタンナノ粒子を同様の用途に用いることもできる。ブルッカイト型二酸化チタンナノ粒子の表面を金属又は金属化合物で修飾することにより、触媒活性が大幅に向上する場合がある。 The brookite-type titanium dioxide nanoparticles thus obtained can be used in the same fields as conventional titanium oxide photocatalysts such as various chemical reactions (for example, oxidation reaction, decomposition reaction of harmful substances) and sterilization. In addition, surface-modified brookite-type titanium dioxide nanoparticles in which a metal or a metal compound (metal ion or the like) is supported on the surface of the brookite-type titanium dioxide nanoparticles can be used for the same purpose. By modifying the surface of brookite-type titanium dioxide nanoparticles with a metal or a metal compound, the catalytic activity may be greatly improved.
ブルッカイト型二酸化チタンナノ粒子の表面への金属又は金属化合物（金属イオン等）の担持法（表面修飾法）としては、固体触媒表面に金属又は金属化合物を担持する場合に用いる公知乃至慣用の手法（例えば、含浸法等）を採用できる。例えば、上記ブルッカイト型二酸化チタンナノ粒子と金属元素源となる化合物（金属硝酸塩等）を水中で混合し、濾過、乾燥し、必要に応じて焼成、還元処理等を施すことにより表面修飾ブルッカイト型二酸化チタンナノ粒子を得ることができる。 As a method (surface modification method) for supporting a metal or a metal compound (metal ion, etc.) on the surface of brookite-type titanium dioxide nanoparticles, a known or conventional method used for supporting a metal or metal compound on the surface of a solid catalyst (for example, , Impregnation method and the like). For example, the surface-modified brookite-type titanium dioxide nanoparticles are mixed by mixing the brookite-type titanium dioxide nanoparticles and the metal element source compound (metal nitrate, etc.) in water, filtering, drying, firing and reducing treatment as necessary. Particles can be obtained.
本発明の有機化合物の酸化方法は、上記のブルッカイト型二酸化チタンナノ粒子の存在下、有機化合物を酸化することを特徴とする。ブルッカイト型二酸化チタンナノ粒子の代わりに、上記の表面修飾ブルッカイト型二酸化チタンナノ粒子を触媒として用いることもできる。 The method for oxidizing an organic compound of the present invention is characterized in that the organic compound is oxidized in the presence of the above brookite-type titanium dioxide nanoparticles. Instead of the brookite-type titanium dioxide nanoparticles, the surface-modified brookite-type titanium dioxide nanoparticles can be used as a catalyst.
前記有機化合物としては、少なくとも１つの被酸化部位を有する有機化合物であれば特に限定されない。被酸化部位を有する有機化合物としては、（A1）ヘテロ原子の隣接位に炭素−水素結合を有するヘテロ原子含有化合物、（A2）炭素−ヘテロ原子二重結合を有する化合物、（A3）メチン炭素原子を有する化合物、（A4）不飽和結合の隣接位に炭素−水素結合を有する化合物、（A5）非芳香族性環状炭化水素、（A6）共役化合物、（A7）アミン類、（A8）芳香族化合物、（A9）直鎖状アルカン、及び（A10）オレフィン類等が挙げられる。 The organic compound is not particularly limited as long as it is an organic compound having at least one site to be oxidized. Examples of the organic compound having an oxidizable site include (A1) a heteroatom-containing compound having a carbon-hydrogen bond adjacent to the heteroatom, (A2) a compound having a carbon-heteroatom double bond, and (A3) a methine carbon atom. (A4) Compound having a carbon-hydrogen bond adjacent to the unsaturated bond, (A5) Non-aromatic cyclic hydrocarbon, (A6) Conjugated compound, (A7) Amines, (A8) Aromatic Compounds, (A9) linear alkanes, and (A10) olefins.
ヘテロ原子の隣接位に炭素−水素結合を有するヘテロ原子含有化合物（A1）としては、（A1-1）第１級若しくは第２級アルコール又は第１級若しくは第２級チオール、（A1-2）酸素原子の隣接位に炭素−水素結合を有するエーテル又は硫黄原子の隣接位に炭素−水素結合を有するスルフィド、（A1-3）酸素原子の隣接位に炭素−水素結合を有するアセタール（ヘミアセタールも含む）又は硫黄原子の隣接位に炭素−水素結合を有するチオアセタール（チオヘミアセタールも含む）などが例示できる。 As the heteroatom-containing compound (A1) having a carbon-hydrogen bond at the adjacent position of the heteroatom, (A1-1) primary or secondary alcohol or primary or secondary thiol, (A1-2) An ether having a carbon-hydrogen bond adjacent to an oxygen atom or a sulfide having a carbon-hydrogen bond adjacent to a sulfur atom, (A1-3) an acetal having a carbon-hydrogen bond adjacent to an oxygen atom (also a hemiacetal) Thioacetal (including thiohemiacetal) having a carbon-hydrogen bond at a position adjacent to a sulfur atom.
前記炭素−ヘテロ原子二重結合を有する化合物（A2）としては、（A2-1）カルボニル基含有化合物、（A2-2）チオカルボニル基含有化合物、（A2-3）イミン類などが挙げられる。 Examples of the compound (A2) having a carbon-heteroatom double bond include (A2-1) carbonyl group-containing compounds, (A2-2) thiocarbonyl group-containing compounds, (A2-3) imines, and the like.
前記メチン炭素原子を有する化合物（A3）には、（A3-1）環の構成単位としてメチン基（すなわち、メチン炭素−水素結合）を含む環状化合物、（A3-2）メチン炭素原子を有する鎖状化合物が含まれる。 The compound (A3) having a methine carbon atom includes (A3-1) a cyclic compound containing a methine group (that is, a methine carbon-hydrogen bond) as a structural unit of the ring, and (A3-2) a chain having a methine carbon atom. Like compounds.
前記不飽和結合の隣接位に炭素−水素結合を有する化合物（A4）としては、（A4-1）芳香族性環の隣接位（いわゆるベンジル位）にメチル基又はメチレン基を有する芳香族化合物、（A4-2）不飽和結合（例えば、炭素−炭素不飽和結合、炭素−酸素二重結合など）の隣接位にメチル基又はメチレン基を有する非芳香族性化合物などが挙げられる。 As the compound (A4) having a carbon-hydrogen bond at the adjacent position of the unsaturated bond, (A4-1) an aromatic compound having a methyl group or a methylene group at the adjacent position (so-called benzyl position) of the aromatic ring, (A4-2) Non-aromatic compounds having a methyl group or a methylene group at an adjacent position of an unsaturated bond (for example, a carbon-carbon unsaturated bond, a carbon-oxygen double bond, etc.), and the like.
前記非芳香族性環状炭化水素（A5）には、（A5-1）シクロアルカン類及び（A5-2）シクロアルケン類が含まれる。 The non-aromatic cyclic hydrocarbon (A5) includes (A5-1) cycloalkanes and (A5-2) cycloalkenes.
前記共役化合物（A6）には、共役ジエン類（A6-1）、α，β−不飽和ニトリル（A6-2）、α，β−不飽和カルボン酸又はその誘導体（例えば、エステル、アミド、酸無水物等）（A6-3）などが挙げられる。 The conjugated compound (A6) includes conjugated dienes (A6-1), α, β-unsaturated nitriles (A6-2), α, β-unsaturated carboxylic acids or derivatives thereof (for example, esters, amides, acids Anhydride, etc.) (A6-3).
前記アミン類（A7）としては、第１級または第２級アミンなどが挙げられる。 Examples of the amines (A7) include primary or secondary amines.
前記芳香族炭化水素（A8）としては、少なくともベンゼン環を１つ有する芳香族化合物、好ましくは少なくともベンゼン環が複数個（例えば、２〜１０個）縮合している縮合多環式芳香族化合物などが挙げられる。 Examples of the aromatic hydrocarbon (A8) include an aromatic compound having at least one benzene ring, preferably a condensed polycyclic aromatic compound in which a plurality of (for example, 2 to 10) benzene rings are condensed. Is mentioned.
前記直鎖状アルカン（A9）としては、炭素数１〜３０程度（好ましくは炭素数１〜２０程度）の直鎖状アルカンが挙げられる。 Examples of the linear alkane (A9) include linear alkanes having about 1 to 30 carbon atoms (preferably about 1 to 20 carbon atoms).
前記オレフィン類（A10）としては、置換基（例えば、ヒドロキシル基、アシルオキシ基等の前記例示の置換基など）を有していてもよいα−オレフィン及び内部オレフィンの何れであってもよく、ジエンなどの炭素−炭素二重結合を複数個有するオレフィン類も含まれる。 The olefins (A10) may be any of α-olefins and internal olefins which may have a substituent (for example, the above-mentioned exemplified substituents such as a hydroxyl group and an acyloxy group), and diene. Olefins having a plurality of carbon-carbon double bonds such as are also included.
上記の被酸化部位を有する有機化合物は単独で用いてもよく、同種又は異種のものを２種以上組み合わせて用いてもよい。 The organic compound having the site to be oxidized may be used alone, or two or more of the same or different types may be used in combination.
本発明の酸化方法において、前記ブルッカイト型二酸化チタンナノ粒子の使用量は、基質として用いる有機化合物１００重量部に対して、例えば１〜１００００重量部、好ましくは１０〜５０００重量部、さらに好ましくは５０〜２０００重量部程度である。 In the oxidation method of the present invention, the amount of the brookite-type titanium dioxide nanoparticles used is, for example, 1 to 10000 parts by weight, preferably 10 to 5000 parts by weight, and more preferably 50 to 50 parts by weight with respect to 100 parts by weight of the organic compound used as the substrate. About 2000 parts by weight.
本発明の方法では、基質としての有機化合物を光照射下に分子状酸素及び／又は過酸化物で酸化することが多い。照射する光としては、通常、３８０ｎｍ未満の紫外線が使用されるが、例えば３８０ｎｍ以上、６５０ｎｍ程度までの長波長の可視光線を使用することもできる。 In the method of the present invention, an organic compound as a substrate is often oxidized with molecular oxygen and / or peroxide under light irradiation. As the light to be irradiated, ultraviolet rays having a wavelength of less than 380 nm are usually used. For example, visible light having a long wavelength from 380 nm to 650 nm can also be used.
分子状酸素としては、純粋な酸素を用いてもよく、窒素、ヘリウム、アルゴン、二酸化炭素などの不活性ガスで希釈した酸素や空気を用いてもよい。分子状酸素の使用量は、基質として用いる有機化合物１モルに対して、例えば０．５モル以上、好ましくは１モル以上である。有機化合物に対して過剰モルの分子状酸素を用いることが多い。 As molecular oxygen, pure oxygen may be used, or oxygen or air diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide may be used. The amount of molecular oxygen used is, for example, 0.5 mol or more, preferably 1 mol or more, with respect to 1 mol of the organic compound used as the substrate. Often an excess of molecular oxygen is used relative to the organic compound.
過酸化物としては、特に限定されず、ペルオキシド、ヒドロペルオキシド等の何れも使用できる。代表的な過酸化物として、過酸化水素、クメンヒドロペルオキシド、ｔ−ブチルヒドロペルオキシド、トリフェニルメチルヒドロペルオキシド、ｔ−ブチルペルオキシド、ベンゾイルペルオキシドなどが挙げられる。上記過酸化水素としては、純粋な過酸化水素を用いてもよいが、取扱性の点から、通常、適当な溶媒、例えば水に希釈した形態（例えば、３０重量％過酸化水素水）で用いられる。過酸化物の使用量は、基質として用いる有機化合物１モルに対して、例えば０．１〜５モル程度、好ましくは０．３〜１．５モル程度である。 The peroxide is not particularly limited, and any of peroxide, hydroperoxide and the like can be used. Representative peroxides include hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, triphenylmethyl hydroperoxide, t-butyl peroxide, benzoyl peroxide, and the like. As the hydrogen peroxide, pure hydrogen peroxide may be used, but from the viewpoint of handleability, it is usually used in a form diluted with an appropriate solvent such as water (for example, 30% by weight hydrogen peroxide). It is done. The usage-amount of a peroxide is about 0.1-5 mol with respect to 1 mol of organic compounds used as a substrate, Preferably it is about 0.3-1.5 mol.
本発明では、分子状酸素と過酸化物のうち一方のみを用いてもよいが、分子状酸素と過酸化物とを組み合わせることにより、反応速度が大幅に向上する場合がある。 In the present invention, only one of molecular oxygen and peroxide may be used, but the reaction rate may be significantly improved by combining molecular oxygen and peroxide.
反応は、通常、溶媒存在下で行われる。該溶媒としては、例えば、ヘキサン、ヘプタン、オクタン、リグロイン、石油エーテル等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、シクロヘプタン等の脂環式炭化水素；エチルエーテル、イソプロピルエーテル、テトラヒドロフラン等のエーテル類；酢酸エチル等のエステル類；、アセトニトリル、プロピオニトリル、ブチロニトリル、ベンゾニトリル等のニトリル類；Ｎ，Ｎ−ジメチルホルムアミド等の非プロトン性極性溶媒；酢酸等の有機酸；水；これらの混合溶媒などが挙げられる。 The reaction is usually performed in the presence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, ligroin and petroleum ether; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cycloheptane; ethers such as ethyl ether, isopropyl ether and tetrahydrofuran. Esters such as ethyl acetate; nitriles such as acetonitrile, propionitrile, butyronitrile, and benzonitrile; aprotic polar solvents such as N, N-dimethylformamide; organic acids such as acetic acid; water; mixed solvents thereof Etc.
反応温度は、反応速度及び反応選択性を考慮して適宜選択できるが、一般には−２０℃〜１００℃程度である。反応は室温付近で行われることが多い。反応はバッチ式、セミバッチ式、連続式などの何れの方法で行ってもよい。 Although reaction temperature can be suitably selected in view of reaction rate and reaction selectivity, it is generally about -20 ° C to 100 ° C. The reaction is often performed near room temperature. The reaction may be carried out by any method such as batch, semi-batch and continuous methods.
上記反応により、有機化合物から対応する酸化開裂生成物（例えば、アルデヒド化合物）、キノン類、ヒドロペルオキシド、ヒドロキシル基含有化合物、カルボニル化合物、カルボン酸などの酸素原子含有化合物などが生成する。例えば、アルコールからは対応するカルボニル化合物（ケトン、アルデヒド）やカルボン酸等が、アルデヒドからは対応するカルボン酸等が生成する。また、アダマンタンからは１−アダマンタノール、２−アダマンタノール、２−アダマンタノンなどが生成する。これらの生成物の生成割合（選択率）は、反応条件等を適宜選択することにより調整できる。 By the above reaction, a corresponding oxidative cleavage product (for example, an aldehyde compound), a quinone, a hydroperoxide, a hydroxyl group-containing compound, a carbonyl compound, a carboxylic acid-containing compound or the like is generated from the organic compound. For example, a corresponding carbonyl compound (ketone, aldehyde) or carboxylic acid is generated from alcohol, and a corresponding carboxylic acid is generated from aldehyde. Further, 1-adamantanol, 2-adamantanol, 2-adamantanone and the like are produced from adamantane. The production ratio (selectivity) of these products can be adjusted by appropriately selecting reaction conditions and the like.
反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段や、これらを組み合わせた分離手段により分離精製できる。また、ブルッカイト型二酸化チタンナノ粒子は濾過により容易に分離でき、分離した触媒は、必要に応じて洗浄等の処理を施した後、リサイクル使用できる。 The reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. Further, the brookite-type titanium dioxide nanoparticles can be easily separated by filtration, and the separated catalyst can be recycled after being subjected to treatment such as washing as necessary.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
実施例１
チタネートナノチューブの粉末（商品名「ＴＮＴ−３５２」、Catalysts & Chemicals Ind. Co. Ltd. 製、比表面積：２４０ｍ2／ｇ）１ｇを２Ｍ過塩素酸水溶液５０ｍＬ中に分散させ、２００℃にて５０時間水熱処理を行った（反応器としてテフロン（登録商標）ボトルを使用）。反応混合液を遠心分離に付し、上澄みを除去し、得られた沈殿物をイオン交換水（「Milli-Q water」）に分散させ、これを遠心分離に付した（５０００ｒｐｍ、３０分）。上澄み（不透明）を濾過し、濾物（濾さい）を１重量％アンモニア水で洗浄し、イオン交換水（「Milli-Q water」）で伝導度が１０μＳ／ｃｍ2以下になるまで洗浄し、６０℃で２時間真空乾燥することにより、ブルッカイト型二酸化チタンナノ粒子を得た。
図１に、水熱処理における時間と各結晶相の比率との関係を示した。横軸は水熱処理の時間、縦軸は各結晶相の比率（重量比率）である。図中、ｆAはアナターゼ相、ｆBはブルッカイト相、ｆRはルチル相を示す。
図２に、得られたブルッカイト型二酸化チタンナノ粒子のＴＥＭ画像を示した。
Example 1
1 g of titanate nanotube powder (trade name “TNT-352”, manufactured by Catalysts & Chemicals Ind. Co. Ltd., specific surface area: 240 m 2 / g) was dispersed in 50 mL of 2M aqueous perchloric acid solution, and 50% at 200 ° C. Hydrothermal treatment was performed for an hour (using a Teflon (registered trademark) bottle as the reactor). The reaction mixture was centrifuged, the supernatant was removed, and the resulting precipitate was dispersed in ion-exchanged water (“Milli-Q water”), which was centrifuged (5000 rpm, 30 minutes). The supernatant (opaque) is filtered, the filtrate (filtered) is washed with 1% by weight ammonia water, and washed with ion-exchanged water (“Milli-Q water”) until the conductivity is 10 μS / cm 2 or less. By vacuum-drying at 60 ° C. for 2 hours, brookite-type titanium dioxide nanoparticles were obtained.
FIG. 1 shows the relationship between the time for hydrothermal treatment and the ratio of each crystal phase. The horizontal axis represents the hydrothermal treatment time, and the vertical axis represents the ratio (weight ratio) of each crystal phase. In the figure, f A represents an anatase phase, f B represents a brookite phase, and f R represents a rutile phase.
FIG. 2 shows a TEM image of the obtained brookite-type titanium dioxide nanoparticles.
実施例２
２Ｍ過塩素酸水溶液の代わりに２Ｍ塩酸を用いた以外は、実施例１と同様にして水熱処理を行った。１時間後の各結晶相の比率（重量比率）は、ブルッカイト相が約５２％、アナターゼ相が約４０％、ルチル相が約８％であり、２０時間後の各結晶相の比率（重量比率）は、ブルッカイト相が約１５％、アナターゼ相が０％、ルチル相が約８５％であった。
Example 2
Hydrothermal treatment was performed in the same manner as in Example 1 except that 2M hydrochloric acid was used instead of the 2M perchloric acid aqueous solution. The ratio (weight ratio) of each crystal phase after 1 hour is about 52% for the brookite phase, about 40% for the anatase phase and about 8% for the rutile phase, and the ratio (weight ratio) for each crystal phase after 20 hours. ) Was about 15% of the brookite phase, 0% of the anatase phase and about 85% of the rutile phase.
実施例３
２Ｍ過塩素酸水溶液の代わりに２Ｍ硝酸水溶液を用いた以外は、実施例１と同様にして水熱処理を行った。５時間後の各結晶相の比率（重量比率）は、ブルッカイト相が約８０％、アナターゼ相が約８％、ルチル相が約１０％であり、２０時間後の各結晶相の比率（重量比率）は、ブルッカイト相が約４０％、アナターゼ相が０％、ルチル相が約６０％であった。
Example 3
Hydrothermal treatment was performed in the same manner as in Example 1 except that a 2M nitric acid aqueous solution was used instead of the 2M perchloric acid aqueous solution. The ratio (weight ratio) of each crystal phase after 5 hours is about 80% for the brookite phase, about 8% for the anatase phase and about 10% for the rutile phase, and the ratio (weight ratio) for each crystal phase after 20 hours. ) Was about 40% of the brookite phase, 0% of the anatase phase and about 60% of the rutile phase.
実施例４
実施例１で得られたブルッカイト型二酸化チタンナノ粒子１００ｍｇをガラス製の皿に拡げて置き、これを内容積１２５ｍＬのテドラーバッグ（空気雰囲気）内に設置した。テドラーバッグ内にアセトアルデヒドを注入し（５００ｐｐｍ）、室温で、ＬＥＤランプ（波長３６５ｎｍ）を１．０ｍＷ／ｃｍ2の強度で照射した。所定時間毎に、テドラーバッグ内のアセトアルデヒド濃度及び二酸化炭素濃度をガスクロマトグラフィーにて分析した。５００分後、二酸化炭素濃度は約１０００ｐｐｍとなった。このブルッカイト型二酸化チタンナノ粒子は、アセトアルデヒド分解反応において、市販のアナターゼ型二酸化チタン（商品名「ＳＴ−０１」、比表面積：３１６ｍ2／ｇ）の約２倍の触媒活性を示した。
Example 4
100 mg of brookite-type titanium dioxide nanoparticles obtained in Example 1 were placed on a glass dish and placed in a Tedlar bag (air atmosphere) having an internal volume of 125 mL. Acetaldehyde was injected into the Tedlar bag (500 ppm), and an LED lamp (wavelength 365 nm) was irradiated at an intensity of 1.0 mW / cm 2 at room temperature. Every predetermined time, the acetaldehyde concentration and the carbon dioxide concentration in the Tedlar bag were analyzed by gas chromatography. After 500 minutes, the carbon dioxide concentration was about 1000 ppm. The brookite-type titanium dioxide nanoparticles exhibited about twice the catalytic activity of commercially available anatase-type titanium dioxide (trade name “ST-01”, specific surface area: 316 m 2 / g) in the acetaldehyde decomposition reaction.
実施例５
実施例１と同様の方法により得たブルッカイト型二酸化チタンナノ粒子１．０ｇを、室温下において硝酸鉄（III）水溶液中で撹拌した後、濾別し、イオン交換水（「Milli-Q water」）で伝導度が１０μＳ／ｃｍ2以下になるまで洗浄し、６０℃で２時間真空乾燥することによって、表面がＦｅ3+（０．０１重量％）で修飾されたブルッカイト型二酸化チタンナノ粒子を得た。
このＦｅ3+（０．０１重量％）表面修飾ブルッカイト型二酸化チタンナノ粒子１００ｍｇをガラス製の皿に拡げて置き、これを内容積１２５ｍＬのテドラーバッグ（空気雰囲気）内に設置した。テドラーバッグ内にアセトアルデヒドを注入し（５００ｐｐｍ）、室温で、紫色発光ダイオード（波長４２０ｎｍ）を１．０ｍＷ／ｃｍ2の強度で照射した。所定時間毎に、テドラーバッグ内のアセトアルデヒド濃度及び二酸化炭素濃度をガスクロマトグラフィーにて分析した。１５００分後、二酸化炭素濃度は約８００ｐｐｍとなった。
なお、Ｆｅ3+（０．０１重量％）修飾ブルッカイト型二酸化チタンナノ粒子の代わりに、表面無修飾のブルッカイト型二酸化チタンナノ粒子を用いて同様の操作を行ったところ、二酸化炭素濃度は約１００ｐｐｍであった。
Example 5
1.0 g of brookite-type titanium dioxide nanoparticles obtained by the same method as in Example 1 was stirred in an aqueous iron (III) nitrate solution at room temperature, filtered, and ion-exchanged water (“Milli-Q water”) The brookite-type titanium dioxide nanoparticles whose surface was modified with Fe 3+ (0.01% by weight) were obtained by washing at 60 ° C. until the conductivity reached 10 μS / cm 2 or less and vacuum drying at 60 ° C. for 2 hours. .
100 mg of this Fe 3+ (0.01 wt%) surface-modified brookite-type titanium dioxide nanoparticles were spread on a glass dish and placed in a Tedlar bag (air atmosphere) having an internal volume of 125 mL. Acetaldehyde was injected into the Tedlar bag (500 ppm), and a purple light emitting diode (wavelength: 420 nm) was irradiated at an intensity of 1.0 mW / cm 2 at room temperature. Every predetermined time, the acetaldehyde concentration and the carbon dioxide concentration in the Tedlar bag were analyzed by gas chromatography. After 1500 minutes, the carbon dioxide concentration was about 800 ppm.
When the same operation was carried out using non-surface modified brookite type titanium dioxide nanoparticles instead of Fe 3+ (0.01% by weight) modified brookite type titanium dioxide nanoparticles, the carbon dioxide concentration was about 100 ppm. It was.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102303905A (en) * | 2011-08-18 | 2012-01-04 | 刘奕 | Method for producing brookite TiO2 in large scale at low cost |
| JP2012254922A (en) * | 2011-05-18 | 2012-12-27 | Daicel Corp | Method for producing transition metal compound supporting titanium oxide |
| JP2015070959A (en) * | 2013-10-03 | 2015-04-16 | 東洋興商株式会社 | Photocatalytic deodorizing device |
| CN112758980A (en) * | 2019-11-06 | 2021-05-07 | 国家纳米科学中心 | TiO 22Nano material, preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012254922A (en) * | 2011-05-18 | 2012-12-27 | Daicel Corp | Method for producing transition metal compound supporting titanium oxide |
| CN102303905A (en) * | 2011-08-18 | 2012-01-04 | 刘奕 | Method for producing brookite TiO2 in large scale at low cost |
| JP2015070959A (en) * | 2013-10-03 | 2015-04-16 | 東洋興商株式会社 | Photocatalytic deodorizing device |
| CN112758980A (en) * | 2019-11-06 | 2021-05-07 | 国家纳米科学中心 | TiO 22Nano material, preparation method and application thereof |
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