JP2005047787A - Titanium dioxide microparticle and method for producing the same - Google Patents
Titanium dioxide microparticle and method for producing the same 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 303
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 146
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000011859 microparticle Substances 0.000 title abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 60
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
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- 239000002994 raw material Substances 0.000 claims abstract description 21
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- 150000001450 anions Chemical class 0.000 claims abstract description 17
- 230000010718 Oxidation Activity Effects 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims description 103
- 239000002245 particle Substances 0.000 claims description 23
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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Abstract
Description
本発明は、可視光活性型光触媒、半導体や光通信の反射膜として好適に用いることができる二酸化チタン微粒子およびその製造方法に関し、特に、可視光の照射に対して活性を示し、このような光触媒活性を利用して、分解、除去、消臭、抗菌、防汚、防曇等の作用を奏することにより、塗料、繊維製品、シックハウス解消剤、工業排水・排ガス等の無害化処理剤、医用材料等に好適に用いることができる、二酸化チタン微粒子およびその製造方法に関する。 The present invention relates to a visible light active photocatalyst, titanium dioxide fine particles that can be suitably used as a reflective film for semiconductors and optical communication, and a method for producing the same, and in particular, exhibits activity against visible light irradiation. By utilizing the activity, it has the effects of decomposing, removing, deodorizing, antibacterial, antifouling, antifogging, etc., thereby making paints, textile products, sick house decontaminants, industrial wastewater / exhaust gas detoxifying agents, medical materials, etc. The present invention relates to titanium dioxide fine particles and a method for producing the same.
二酸化チタン等の半導体粒子に、そのバンドギャップ以上のエネルギーを有する光を照射すると、光励起により生成した電子および正孔が、該半導体粒子表面に移動し、周囲に存在するイオン種や分子種に作用して、光触媒反応と呼ばれる様々な反応を引き起こす。
特に、二酸化チタン微粒子は、その表面に生じた正孔が、強力な酸化力を有していることから、塗料、繊維製品、シックハウスの解消、工業排水・排ガスの無害化処理剤等への応用が種々提案されており、一部は既に実用化されている。
When semiconductor particles such as titanium dioxide are irradiated with light having energy greater than the band gap, electrons and holes generated by photoexcitation move to the surface of the semiconductor particles and act on ionic and molecular species present in the surroundings. This causes various reactions called photocatalytic reactions.
In particular, the fine particles of titanium dioxide have a strong oxidizing power on the surface, so they can be applied to paints, textiles, elimination of sick houses, industrial wastewater and exhaust gas detoxifying agents, etc. Have been proposed, and some have already been put into practical use.
従来、光触媒技術分野において使用されている二酸化チタン微粒子は、アナターゼ型またはルチル型の結晶質である。
アナターゼ型またはルチル型の二酸化チタンのバンドギャップは、それぞれ３．２ｅＶ（波長３８７．５ｎｍに相当）または３．０ｅＶ（波長４１３．３ｎｍに相当）であるため、励起光としては、それぞれ波長３８７．５ｎｍ以下または波長４１３．３ｎｍ以下の短波長光である紫外線が利用されているに過ぎず、可視光等の光は利用されていなかった。
Conventionally, the titanium dioxide fine particles used in the photocatalytic technical field are crystalline of anatase type or rutile type.
Since the band gap of anatase type or rutile type titanium dioxide is 3.2 eV (corresponding to a wavelength of 387.5 nm) or 3.0 eV (corresponding to a wavelength of 413.3 nm), respectively, the excitation light has a wavelength of 387. Only ultraviolet rays, which are short-wavelength light of 5 nm or less or a wavelength of 413.3 nm or less, are used, and light such as visible light is not used.
このため、前記結晶質の二酸化チタンは、光の中に紫外線がほとんど存在しない屋内等で使用される内装塗料、繊維製品、シックハウス解消剤等の用途においては、機能を果たすことは困難であり、実際上、用途範囲は制限されていた。
これに対して、最近では、太陽光および人工光を効率よく利用する目的で、可視光の照射により触媒活性を示す二酸化チタンの開発が種々検討されるようになってきた。
For this reason, the crystalline titanium dioxide is difficult to fulfill its function in applications such as interior paints, textile products, sick house deterrents, etc. used indoors where there is almost no ultraviolet light in the light, In practice, the range of applications has been limited.
On the other hand, recently, for the purpose of efficiently using sunlight and artificial light, various developments of titanium dioxide exhibiting catalytic activity by irradiation with visible light have been studied.
例えば、特許文献１には、高減圧下で、水素プラズマ処理、希ガス類元素プラズマ処理を行ったり、希ガス類元素のイオン注入、または、真空下での高温加熱等の方法を用いて、アナターゼ型の二酸化チタンの結晶格子構造を酸素欠乏型とし、これにより、可視領域の光照射での触媒活性を発現させた可視光活性型光触媒およびその製法が開示されている。 For example, Patent Document 1 discloses that anatase-type dioxide dioxide is obtained by performing a hydrogen plasma treatment or a rare gas element plasma treatment under high vacuum, ion implantation of a rare gas element, or high-temperature heating under a vacuum. A visible light active photocatalyst having a titanium crystal lattice structure which is oxygen-deficient and thereby exhibiting catalytic activity in the light irradiation in the visible region and a method for producing the same are disclosed.
また、二酸化チタンに窒素ドープすることによる可視光応答型の二酸化チタン光触媒もある（非特許文献１参照）。例えば、特許文献２には、結晶内に窒素が存在する特定の二酸化チタン結晶が可視光の照射に対して触媒活性を示すことが開示されている。
窒素ドープされた二酸化チタンは、ドープされた窒素が、格子間の隙間に入った状態、または、格子酸素のサイトに窒素が置換された形で入っている状態の構造となっている。
このような窒素ドープされた二酸化チタンは、塩化チタン溶液をアンモニア水中で加水分解することにより、または、二酸化チタンをアンモニアガス中で加熱することにより合成することができる。
There is also a visible light responsive titanium dioxide photocatalyst by doping nitrogen dioxide into titanium dioxide (see Non-Patent Document 1). For example, Patent Document 2 discloses that a specific titanium dioxide crystal in which nitrogen is present in the crystal exhibits catalytic activity against visible light irradiation.
Nitrogen-doped titanium dioxide has a structure in which doped nitrogen enters a gap between lattices or a state in which nitrogen is substituted at lattice oxygen sites.
Such nitrogen-doped titanium dioxide can be synthesized by hydrolyzing a titanium chloride solution in ammonia water or by heating titanium dioxide in ammonia gas.
上記した酸素欠乏型または窒素ドープされた二酸化チタンにおいては、酸素欠乏欠陥またはＴｉ−Ｎの結合により、二酸化チタン光触媒に可視光活性がもたらされると考えられる。 In the above oxygen-deficient or nitrogen-doped titanium dioxide, it is considered that visible light activity is brought to the titanium dioxide photocatalyst by oxygen-deficient defects or Ti—N bonds.
しかしながら、上記した酸素欠乏型または窒素ドープされた二酸化チタンは、可視光による光触媒活性が必ずしも十分に高いとは言えず、また、光触媒活性の安定性に劣る等の課題を有していた。 However, the above oxygen-deficient or nitrogen-doped titanium dioxide cannot be said to have a sufficiently high photocatalytic activity by visible light, and has problems such as poor photocatalytic activity stability.
例えば、窒素ドープされた二酸化チタンのＴｉ−Ｎ結合に基づくＸＰＳ（Ｘ線光電子分光法）分析によるピークは、空気中での熱処理により消失するという報告もあることから、上記のような技術的課題が生じる原因としては、空気と接触している粒子表面においては、酸素欠乏欠陥またはＴｉ−Ｎ結合が不安定であることによるものと推測される。 For example, there is a report that a peak by XPS (X-ray photoelectron spectroscopy) analysis based on a Ti-N bond of nitrogen-doped titanium dioxide disappears by heat treatment in air. It is estimated that this is caused by oxygen deficiency defects or unstable Ti-N bonds on the particle surface in contact with air.
本発明は、上記技術的課題を解決するためになされたものであり、可視光照射に対して高い光触媒活性を示すとともに、その光触媒活性が、安定性、持続性に優れている可視光活性型光触媒およびその製造方法を提供することを目的とするものである。 The present invention has been made to solve the above technical problem, and exhibits a high photocatalytic activity for visible light irradiation, and its photocatalytic activity is excellent in stability and sustainability. An object of the present invention is to provide a photocatalyst and a method for producing the same.
本発明に係る二酸化チタン微粒子は、二酸化チタンを主成分とする粒子であって、少なくとも窒素および炭素を含む２種類以上のアニオンがドープされていることを特徴とする。
このように構成された二酸化チタン微粒子は、従来の酸素欠乏型または窒素ドープされた二酸化チタンによる可視光活性型光触媒に比べて、より優れた光触媒活性を示し、しかも、その光触媒活性は、安定性、持続性に優れたものである。
The titanium dioxide fine particles according to the present invention are particles mainly composed of titanium dioxide, and are characterized by being doped with two or more kinds of anions containing at least nitrogen and carbon.
The titanium dioxide fine particles constructed in this way exhibit a superior photocatalytic activity as compared with conventional visible light active photocatalysts using oxygen-deficient or nitrogen-doped titanium dioxide, and the photocatalytic activity is stable. It has excellent sustainability.
前記微粒子における二酸化チタン成分の含有量は、８０重量％以上であることが好ましい。
高い光触媒活性を保持させる観点から、二酸化チタン微粒子の主成分である二酸化チタン成分の含有量を規定したものである。
The content of the titanium dioxide component in the fine particles is preferably 80% by weight or more.
From the viewpoint of maintaining high photocatalytic activity, the content of the titanium dioxide component, which is the main component of the titanium dioxide fine particles, is defined.
また、前記二酸化チタン微粒子においては、化学式ＴｉＯ2-xＮxＮyＡ（ただし、Ｎx：二酸化チタンの結晶の酸素サイトに入っている窒素、Ｎy：二酸化チタンの結晶の格子間に入っている窒素、Ａ：二酸化チタンの結晶にドープされた炭素および他のアニオンを示す。）で表されるものであることが好ましい。
二酸化チタンがこのような構造をとることにより、可視光照射に対する高い光触媒活性を発揮することができる。
Further, in the above titanium dioxide fine particles, chemical formula TiO 2-x N x N y A ( however, N x: nitrogen contained in the oxygen site of crystalline titanium dioxide, N y: entered between lattices of titanium dioxide crystals Nitrogen, A: carbon doped with titanium dioxide crystals and other anions are preferred.
When titanium dioxide has such a structure, high photocatalytic activity for visible light irradiation can be exhibited.
さらに、前記窒素および炭素の各濃度は、５０ｐｐｍ以上であることが好ましい。
高い光触媒活性およびその安定性、持続性等の観点から、窒素および炭素のドーパント濃度を規定したものである。
Further, the concentrations of nitrogen and carbon are preferably 50 ppm or more.
From the viewpoint of high photocatalytic activity and its stability and sustainability, the dopant concentrations of nitrogen and carbon are defined.
また、前記二酸化チタン微粒子は、粒径が１μｍ以下であることが好ましい。
本発明に係る二酸化チタン微粒子は、十分な光触媒活性の発現および溶剤等への良好な分散性等を担保する等の観点から、このような微粒子であることが好ましい。
The titanium dioxide fine particles preferably have a particle size of 1 μm or less.
The titanium dioxide fine particles according to the present invention are preferably such fine particles from the viewpoint of ensuring sufficient photocatalytic activity and ensuring good dispersibility in a solvent or the like.
特に、前記微粒子は、長径１０ｎｍ以上６０ｎｍ以下の長球状であることが好ましい。 In particular, the fine particles are preferably oblong with a major axis of 10 nm to 60 nm.
前記二酸化チタン微粒子は、波長４００ｎｍ以上６００ｎｍ以下の可視光の照射下において、イソプロパノール（ＩＰＡ）酸化活性を示すものである。
可視光の照射下において、ＩＰＡ酸化活性を示すことにより、シックハウスの原因と言われているホルムアルデヒド等のアルデヒド類ガス、車の排ガスＮＯX等の環境汚染物質、ダイオキシン等の環境ホルモン等の人体を害する物質を分解・除去する等の可視光活性型光触媒としての優れた機能が発揮される。
したがって、本発明に係る二酸化チタン微粒子は、そのまま可視光活性型光触媒として好適に用いることができる。
The titanium dioxide fine particles exhibit isopropanol (IPA) oxidation activity under irradiation with visible light having a wavelength of 400 nm to 600 nm.
Under the irradiation of visible light, by showing IPA oxidation activity, aldehyde gas such as formaldehyde, which is said to cause sick house, environmental pollutants of the flue gas NO X like cars, the human body such as environmental hormones such as dioxin Excellent functions as a visible light active photocatalyst such as decomposition and removal of harmful substances are exhibited.
Therefore, the titanium dioxide fine particles according to the present invention can be suitably used as a visible light active photocatalyst as it is.
また、上記のような二酸化チタン微粒子を得るための本発明に係る製造方法は、二酸化チタン原料微粒子を、Ｎ含有ガスを含む還元性ガス雰囲気下、５００℃以上６２０℃以下で熱処理することにより得ることを特徴とする。
このような製造方法によれば、Ｎがドープされた上記のような二酸化チタン微粒子を容易かつ均質に製造することができる。
Further, the production method according to the present invention for obtaining the titanium dioxide fine particles as described above is obtained by heat-treating the titanium dioxide raw material fine particles at 500 ° C. or more and 620 ° C. or less in a reducing gas atmosphere containing N-containing gas. It is characterized by that.
According to such a production method, the above-described titanium dioxide fine particles doped with N can be produced easily and uniformly.
あるいはまた、二酸化チタン原料微粒子を、Ｎ、ＣおよびＨを含むガス雰囲気下、または、ＮＨ3ガスおよびＣを含むガス雰囲気下、５００℃以上６２０℃以下で熱処理してもよい。
上記のようなガス雰囲気下で熱処理することにより、二酸化チタンに、Ｎ、Ｃ、Ｈを均質にドープさせた二酸化チタン微粒子を容易に得ることができる。
Alternatively, the titanium dioxide raw material fine particles may be heat-treated at 500 ° C. or more and 620 ° C. or less in a gas atmosphere containing N, C, and H or a gas atmosphere containing NH 3 gas and C.
By performing heat treatment in the gas atmosphere as described above, titanium dioxide fine particles in which titanium dioxide is uniformly doped with N, C, and H can be easily obtained.
上記製造方法においては、前記二酸化チタン原料微粒子は、平均粒径１０ｎｍ以下、比表面積が３００ｍ2／ｇ以上であることが好ましい。
原料として、このような二酸化チタン原料微粒子を用いることにより、単位体積当たりにＮを多量にドープすることができ、かつ、得られる二酸化チタン微粒子の光触媒反応に寄与する表面積も大きくすることができる。
In the said manufacturing method, it is preferable that the said titanium dioxide raw material fine particle has an average particle diameter of 10 nm or less and a specific surface area of 300 m < 2 > / g or more.
By using such titanium dioxide raw material fine particles as a raw material, a large amount of N can be doped per unit volume, and the surface area contributing to the photocatalytic reaction of the obtained titanium dioxide fine particles can be increased.
上述のとおり、本発明に係る二酸化チタン微粒子は、従来の可視光活性型光触媒に比べて、可視光照射に対して高い光触媒活性を示すとともに、その光触媒活性は、安定性、持続性に優れたものである。
このため、本発明に係る二酸化チタン微粒子は、その光触媒活性を利用して、分解、除去、消臭、抗菌、防汚、防曇等の作用を奏することにより、塗料、繊維製品、シックハウス解消剤、建材、自動車等への内装材、家具、家電製品、住宅設備、食器等の防汚、消臭、除菌のため、あるいは、工業排水・排ガス等の無害化処理剤、医用材料等の様々な用途に好適に用いることができる。
また、本発明に係る二酸化チタン微粒子は、安定しており、半導体としても好適に使用することができ、さらに、窒素ドープにより、従来の二酸化チタン粒子とは屈折率が異なるものであることから、光通信用の反射膜等としても好適に使用することができる。
また、本発明に係る製造方法によれば、上記のような二酸化チタン微粒子を容易かつ均質に得ることができる。
As described above, the titanium dioxide fine particles according to the present invention exhibit higher photocatalytic activity for visible light irradiation than conventional visible light active photocatalysts, and the photocatalytic activity is excellent in stability and sustainability. Is.
For this reason, the titanium dioxide fine particles according to the present invention exhibit the effects of decomposition, removal, deodorization, antibacterial, antifouling, antifogging, etc. by utilizing the photocatalytic activity, thereby providing a paint, a textile product, a thick house eliminating agent. Various materials such as anti-fouling, deodorizing, and sterilization of building materials, interior materials for automobiles, furniture, home appliances, housing equipment, tableware, etc. It can be suitably used for various applications.
In addition, the titanium dioxide fine particles according to the present invention are stable and can be suitably used as a semiconductor, and further, by nitrogen doping, the refractive index is different from that of conventional titanium dioxide particles. It can also be suitably used as a reflective film for optical communication.
Moreover, according to the manufacturing method which concerns on this invention, the above titanium dioxide microparticles | fine-particles can be obtained easily and uniformly.
以下、本発明をより詳細に説明する。
本発明に係る二酸化チタン微粒子は、二酸化チタンを主成分とする粒子であって、少なくとも窒素および炭素を含む２種類以上のアニオンがドープされているものである。
このように、少なくとも窒素および炭素の２種類のアニオンがドープされた二酸化チタンは、従来の酸素欠乏型または窒素ドープされた二酸化チタンとは異なる構成を有しており、このような従来の可視光活性型光触媒に比べて、より優れた光触媒活性を示すものである。しかも、その光触媒活性の安定性、持続性に優れており、空気と接触した場合であっても容易に失活することはない。
なお、紫外線照射に対する光触媒活性も、従来の二酸化チタン光触媒と同程度以上の性能を示す。
Hereinafter, the present invention will be described in more detail.
The titanium dioxide fine particles according to the present invention are particles mainly composed of titanium dioxide and doped with two or more kinds of anions containing at least nitrogen and carbon.
Thus, titanium dioxide doped with at least two types of anions, nitrogen and carbon, has a different structure from conventional oxygen-deficient or nitrogen-doped titanium dioxide. Compared with an active photocatalyst, the photocatalytic activity is more excellent. In addition, the photocatalytic activity is excellent in stability and sustainability, and is not easily deactivated even when it comes into contact with air.
In addition, the photocatalytic activity with respect to ultraviolet irradiation also shows the same or better performance as the conventional titanium dioxide photocatalyst.
前記微粒子における二酸化チタン成分の含有量は、８０重量％以上であることが好ましく、より好ましくは、９５重量％以上である。
二酸化チタン成分の含有量が８０重量％未満である場合は、十分な光触媒活性が得られない。
したがって、２０重量％未満の範囲であれば、二酸化チタンの可視光照射による光触媒活性を損なわない限り、他の無機化合物等を混合した複合粒子を用いることができる。
二酸化チタンに混合される無機化合物としては、例えば、シリカ、アルミナ、ジルコニア、マグネシア、酸化亜鉛等を挙げることができる。
The content of the titanium dioxide component in the fine particles is preferably 80% by weight or more, and more preferably 95% by weight or more.
When the content of the titanium dioxide component is less than 80% by weight, sufficient photocatalytic activity cannot be obtained.
Therefore, in the range of less than 20% by weight, composite particles in which other inorganic compounds are mixed can be used as long as the photocatalytic activity of titanium dioxide by visible light irradiation is not impaired.
Examples of the inorganic compound mixed with titanium dioxide include silica, alumina, zirconia, magnesia, zinc oxide and the like.
一般に、二酸化チタンには、ルチル型（正方晶系）、アナターゼ型（正方晶系）、ブルッカイト型（斜方晶系）の３種の変態があり、いずれもチタン原子に酸素原子が６配位した、ゆがんだ八面体の稜が共有された構造を有している。本発明においては、このうち、光触媒活性を発現させる観点から、ルチル型またはアナターゼ型のものを原料微粒子として用いることが好ましく、特に、アナターゼ型が好ましい。
また、窒素および炭素を含む２種以上のアニオンをドープした後においても、同様に、アナターゼ型であることが特に好ましい。
In general, titanium dioxide has three types of transformation: rutile type (tetragonal system), anatase type (tetragonal system), and brookite type (orthorhombic system). It has a structure in which the ridges of the distorted octahedron are shared. In the present invention, from the viewpoint of developing photocatalytic activity, it is preferable to use a rutile type or anatase type as raw material fine particles, and an anatase type is particularly preferable.
Further, even after doping with two or more kinds of anions containing nitrogen and carbon, the anatase type is particularly preferable.
本発明においては、この二酸化チタンを主成分とする原料微粒子に、少なくとも窒素および炭素を含む２種類以上のアニオンがドープすることにより、二酸化チタン微粒子を得る。
ドーパント濃度は、窒素および炭素のそれぞれについて、５０ｐｐｍ以上であることが好ましく、より好ましくは、１５０ｐｐｍ以上２５０００ｐｐｍ以下である。
前記各ドーパント濃度が５０ｐｐｍ未満である場合は、可視光照射に対する十分な光触媒活性が得られず、特に、初期活性の立ち上がりが遅く、しかも、立ち上がり勾配が小さく、可視光の強度や用途等によっては、その目的を十分に達成することが困難な場合がある。
In the present invention, titanium dioxide fine particles are obtained by doping the raw material fine particles mainly composed of titanium dioxide with two or more kinds of anions containing at least nitrogen and carbon.
The dopant concentration is preferably 50 ppm or more and more preferably 150 ppm or more and 25000 ppm or less for each of nitrogen and carbon.
When the concentration of each dopant is less than 50 ppm, sufficient photocatalytic activity for visible light irradiation cannot be obtained, and in particular, the initial activity rises slowly, and the rise gradient is small, depending on the intensity and use of visible light. , It may be difficult to achieve its objectives sufficiently.
上記のアニオンドープにおいては、必須ドーパントである窒素アニオンおよび炭素アニオン以外に、第３のアニオンまたはそれ以上のアニオンをドーピングしてもよい。
ドープされるアニオンの種類は、特に限定されないが、例えば、硫黄（Ｓ）、セレン（Ｓｅ）、リン（Ｐ）、ヒ素（Ａｓ）、ケイ素（Ｓｉ）、ホウ素（Ｂ）、フッ素（Ｆ）、塩素（Ｃｌ）、臭素（Ｂｒ）等のアニオンを挙げることができる。
In the above-mentioned anion doping, a third anion or higher anions may be doped in addition to the nitrogen anion and carbon anion which are essential dopants.
The kind of anion to be doped is not particularly limited. For example, sulfur (S), selenium (Se), phosphorus (P), arsenic (As), silicon (Si), boron (B), fluorine (F), Anions such as chlorine (Cl) and bromine (Br) can be mentioned.
上記窒素、炭素等のアニオンをドーピングする方法としては、特に限定されるものではなく、通常、この種のドープにおいて用いられる、熱拡散法、レーザドーピング法、プラズマドーピング法、イオン注入法等の方法を採用して差し支えない。
具体的には、イオン注入装置を用いて、窒素アニオンや炭素アニオン源からの加速イオンを二酸化チタンターゲットに打ち込む方法により行うことができる。また、シアン（ＨＣＮ）、シアン酸もしくはイソシアン酸（ＨＯＣＮ）、低級アミン（ＲＮＨ2、Ｒ2ＮＨ、Ｒ3Ｎ）、アゾ、ジアゾ化合物等を含有する溶液、または、これらとアンモニア（ＮＨ3）とを含有する溶液中で、塩化チタン（ＴｉＣｌ4）等の溶液状ハロゲン化チタンを加水分解する方法を用いることもできる。あるいはまた、シアン、シアン酸またはイソシアン酸、低級アミン等またはこれらとアンモニアとを含有する窒素またはアルゴン等の不活性ガス気流中で、または、各種炭化水素とアンモニアとの混合ガス気流中で、二酸化チタン原料微粒子を熱処理（アニール）する方法等によっても行うことができる。
The method for doping anions such as nitrogen and carbon is not particularly limited, and is usually a method such as a thermal diffusion method, a laser doping method, a plasma doping method, or an ion implantation method used in this kind of doping. Can be used.
Specifically, it can be performed by a method of implanting accelerated ions from a nitrogen anion or a carbon anion source into a titanium dioxide target using an ion implantation apparatus. Further, solutions containing cyan (HCN), cyanic acid or isocyanic acid (HOCN), lower amines (RNH 2 , R 2 NH, R 3 N), azo, diazo compounds, and the like, and ammonia (NH 3 ) A method of hydrolyzing a solution-like titanium halide such as titanium chloride (TiCl 4 ) in a solution containing the above can also be used. Alternatively, in a stream of inert gas such as nitrogen or argon containing cyan, cyanic acid or isocyanic acid, lower amine or the like and ammonia, or in a mixed gas stream of various hydrocarbons and ammonia, It can also be performed by a method of heat-treating (annealing) the titanium raw material fine particles.
なお、窒素アニオンと炭素アニオンとは、それぞれ別の化合物の分解によってドープしてもよい。このとき、窒素アニオンと炭素アニオンのドーピングは、同時でも、逐次でもよく、また、ドープ時期についても、その態様に応じて、粒子形成時または形成後のいずれであってもよい。 Note that the nitrogen anion and the carbon anion may be doped by decomposition of different compounds. At this time, the doping of the nitrogen anion and the carbon anion may be performed simultaneously or sequentially, and the doping time may be either during grain formation or after grain formation depending on the mode.
従来の酸素欠乏型二酸化チタンは、化学式で表すとＴｉＯ2-xである。
これに対して、本発明に係る二酸化チタン微粒子は、化学式で表すと、ＴｉＯ2-xＮxＮyＡである。ここで、Ｎxは二酸化チタンの結晶の酸素サイトに入っている窒素、Ｎyは二酸化チタンの結晶の格子間に入っている窒素、Ａは二酸化チタンの結晶にドープされた炭素および他のアニオンを意味する。
二酸化チタンがこのような構造をとることにより、可視光照射に対する高い光触媒活性を発揮することができるものと考えられる。
Conventional oxygen-deficient titanium dioxide is TiO 2-x in chemical formula.
On the other hand, the titanium dioxide fine particles according to the present invention are TiO 2-x N x N y A in chemical formula. Where N x is nitrogen contained in the oxygen site of the titanium dioxide crystal, N y is nitrogen contained in the lattice of the titanium dioxide crystal, and A is carbon and other anions doped in the titanium dioxide crystal. Means.
It is considered that when titanium dioxide has such a structure, it can exhibit high photocatalytic activity for visible light irradiation.
前記二酸化チタン微粒子（一次粒子）の粒径は、十分な光触媒活性および溶媒への分散性等の観点から、１μｍ以下であることが好ましく、より好ましくは、０．００１μｍ以上１μｍ以下である。
このような粒径範囲にある二酸化チタン微粒子は、塗料用途等にも、好適に用いることができる。
The particle diameter of the titanium dioxide fine particles (primary particles) is preferably 1 μm or less, more preferably 0.001 μm or more and 1 μm or less from the viewpoint of sufficient photocatalytic activity and dispersibility in a solvent.
Titanium dioxide fine particles in such a particle size range can be suitably used for coating applications and the like.
特に、上記のような優れた可視光活性を示す本発明に係る二酸化チタン微粒子は、一次粒子形状が、長径１０ｎｍ以上１００ｎｍ以下の長球状として好適に得ることができる。前記微粒子の長径は３０〜６０ｎｍ程度であることがより好ましく、３０ｎｍ以上４０ｎｍ以下であることが、特に好ましい。
また、前記一次粒子は、短径と長径の比が１：２〜４程度であることが好ましい。
In particular, the titanium dioxide fine particles according to the present invention exhibiting excellent visible light activity as described above can be suitably obtained as an oval having a major particle diameter of 10 nm or more and 100 nm or less. The major axis of the fine particles is more preferably about 30 to 60 nm, and particularly preferably 30 nm to 40 nm.
The primary particles preferably have a minor axis to major axis ratio of about 1: 2 to 4.
本発明に係る二酸化チタン微粒子は、波長４００ｎｍ以上６００ｎｍ以下の可視光の照射下において、イソプロパノール（ＩＰＡ）酸化活性を示すものである。
ＩＰＡの酸化反応は光触媒活性の評価の標準的な方法の一つとして知られている。ＩＰＡは酸化されると、アセトンを生成する。さらに、酸化反応が進行すると、最終的には、二酸化炭素と水を生成する。
このような可視光の照射下におけるＩＰＡの酸化反応の促進作用、すなわち、ＩＰＡ酸化活性を示すことは、シックハウスの原因と言われているホルムアルデヒド等のアルデヒド類ガス、車の排ガスＮＯX等の環境汚染物質、ダイオキシン等の環境ホルモン等の人体を害する物質を分解・除去する能力を持つことを意味し、可視光活性型光触媒としての優れた機能が発揮されると言える。
したがって、本発明に係る二酸化チタン微粒子は、可視光活性型光触媒として好適に用いることができる。
The titanium dioxide fine particles according to the present invention exhibit isopropanol (IPA) oxidation activity under irradiation with visible light having a wavelength of 400 nm or more and 600 nm or less.
The oxidation reaction of IPA is known as one of standard methods for evaluating photocatalytic activity. When IPA is oxidized, it produces acetone. Further, when the oxidation reaction proceeds, carbon dioxide and water are finally generated.
Promoting action of oxidation of IPA under irradiation of such visible light, i.e., to exhibit IPA oxidation activity, aldehydes gas such as formaldehyde, which is said to cause sick house, car exhaust gas NO X of environmental It means that it has the ability to decompose and remove pollutants, environmental hormones such as dioxins, and other substances that harm the human body, and it can be said that it exhibits excellent functions as a visible light active photocatalyst.
Therefore, the titanium dioxide fine particles according to the present invention can be suitably used as a visible light active photocatalyst.
上記のような本発明に係る二酸化チタン微粒子は、二酸化チタン原料微粒子を、Ｎ含有ガスを含む還元性ガス雰囲気下、５００℃以上６２０℃以下で熱処理することにより得ることができる。
このような製造方法によれば、上記のような可視光照射に対して優れた光触媒活性を示す、Ｎがドープされた二酸化チタン微粒子を容易かつ均質に製造することができる。
The titanium dioxide fine particles according to the present invention as described above can be obtained by heat-treating titanium dioxide raw material fine particles at 500 ° C. or more and 620 ° C. or less in a reducing gas atmosphere containing N-containing gas.
According to such a production method, it is possible to easily and uniformly produce N-doped titanium dioxide fine particles that exhibit excellent photocatalytic activity for visible light irradiation as described above.
このとき、二酸化チタン原料微粒子の一次粒子は、平均粒径が１０ｎｍ以下の微粒子であることが好ましい。また、この一次粒子の比表面積は、３００ｍ2／ｇ以上であることが好ましい。
このような比表面積が大きい二酸化チタン原料微粒子を原料とすることにより、単位体積当りにＮを多量にドープすることができ、しかも、得られる二酸化チタン微粒子の光触媒反応に寄与する表面積も大きくすることができる。
At this time, the primary particles of the titanium dioxide raw material fine particles are preferably fine particles having an average particle size of 10 nm or less. Moreover, it is preferable that the specific surface area of this primary particle is 300 m < 2 > / g or more.
By using such titanium dioxide raw material fine particles having a large specific surface area as a raw material, a large amount of N can be doped per unit volume, and the surface area contributing to the photocatalytic reaction of the obtained titanium dioxide fine particles should be increased. Can do.
上記のような二酸化チタン微粒子の製造方法における熱処理温度は、５００℃以上６２０℃以下であることが好ましい。
５００℃未満または６２０℃を超える温度で熱処理を行った場合は、光触媒の十分な可視光活性が得られない。
上記熱処理温度は、より好ましくは、５３０℃以上５９０℃以下である。
The heat treatment temperature in the method for producing titanium dioxide fine particles as described above is preferably 500 ° C. or more and 620 ° C. or less.
When heat treatment is performed at a temperature lower than 500 ° C. or higher than 620 ° C., sufficient visible light activity of the photocatalyst cannot be obtained.
The heat treatment temperature is more preferably 530 ° C. or higher and 590 ° C. or lower.
また、上記熱処理は、二酸化チタン原料微粒子にＮをドープさせるために、Ｎ含有ガスを含む還元性ガス雰囲気下で行われることが好ましい。
前記Ｎ含有ガスとしては、Ｎ2、ＮＨ3、ＮＯ、ＮＯ2等を用いることができる。
また、還元性ガス雰囲気とするために、上記Ｎ含有ガスとＨ2等との混合ガスを用いてもよい。
The heat treatment is preferably performed in a reducing gas atmosphere containing an N-containing gas in order to dope the titanium dioxide raw material fine particles with N.
As the N-containing gas, N 2 , NH 3 , NO, NO 2 or the like can be used.
In order to obtain a reducing gas atmosphere, a mixed gas of the N-containing gas and H 2 or the like may be used.
また、二酸化チタン原料微粒子にＣ、Ｈもドープさせるために、Ｎ、ＣおよびＨを含むガス雰囲気下、または、ＮＨ3ガスおよびＣを含むガス雰囲気下で、熱処理を行ってよい。
前記Ｃを含むガスとしては、Ｈを含むメタン、エタン、プロパン、ブタン等の炭化水素ガスの他、一酸化炭素、二酸化炭素等が挙げられるが、特に、炭化水素ガスが好適に用いられる。
上記のようなガス雰囲気は、１種類のガスを用いてもよく、また、複数種類のガスを混合して形成してもよい。また、不活性ガスを混合しても差し支えない。
Further, in order to dope C and H to the titanium dioxide raw material fine particles, heat treatment may be performed in a gas atmosphere containing N, C and H or a gas atmosphere containing NH 3 gas and C.
Examples of the gas containing C include hydrocarbon gas such as methane, ethane, propane, and butane containing H, carbon monoxide, carbon dioxide, and the like. In particular, hydrocarbon gas is preferably used.
As the above gas atmosphere, one kind of gas may be used, or a plurality of kinds of gases may be mixed and formed. Further, an inert gas may be mixed.
例えば、ＮＨ3ガスおよび炭化水素ガスの混合ガスを用いる場合には、炭化水素ガスは、ＮＨ3ガスよりも少ないことが好ましく、ＮＨ3ガスに対して２〜７０％であることが好ましい。より好ましくは、５〜５０％である。 For example, in the case of using NH 3 gas and a mixed gas of hydrocarbon gas, the hydrocarbon gas is preferably less than the NH 3 gas is preferably 2 to 70% with respect to NH 3 gas. More preferably, it is 5 to 50%.
以下、本発明を実施例に基づきさらに具体的に説明するが、本発明は下記の実施例により制限されるものではない。
［実施例１］
窒素３０００ｐｐｍおよび炭素１５０ｐｐｍをドープした二酸化チタン微粒子（短径約１０ｎｍ、長径約３０ｎｍの長球状の一次粒子）を合成した。
この二酸化チタン微粒子について、可視光に対する光触媒活性を評価した。
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited by the following Example.
[Example 1]
Titanium dioxide fine particles doped with 3000 ppm nitrogen and 150 ppm carbon (primary spherical particles having a minor axis of about 10 nm and a major axis of about 30 nm) were synthesized.
The photocatalytic activity for visible light was evaluated for the titanium dioxide fine particles.
この可視光活性評価試験は、下記の方法により行った。
まず、上記により合成した二酸化チタン微粒子０．２ｇを水に分散させて、これを１０ｃｍ×１０ｃｍの石英ガラス板に塗布し、５０℃で一晩乾燥させた。
次に、この石英ガラス板を、容積１リットルのテドラーバッグに入れた後、イソプロパノール（ＩＰＡ）蒸気を含んだ空気をバッグ中に１時間循環させ、二酸化チタン微粒子のガス吸着を飽和させた。
この状態を可視光照射前の状態として、バッグ中のＩＰＡおよびアセトンの濃度をガスクロマトグラフィにより測定したところ、ＩＰＡは１５００ｐｐｍ、アセトンは未検出（ＮＤ）であった。
そして、前記テドラーバッグを、４１０ｎｍより短波長の紫外線をカットするカバーを付けた蛍光灯により、波長４２０ｎｍ、強度０．５ｍＷ／ｃｍ2で５時間照射した。照射開始３０分毎に、ＩＰＡ濃度およびＩＰＡの酸化により生成したアセトンの濃度を測定した。
この結果を表１に示す。
This visible light activity evaluation test was performed by the following method.
First, 0.2 g of the titanium dioxide fine particles synthesized as described above were dispersed in water, applied to a 10 cm × 10 cm quartz glass plate, and dried at 50 ° C. overnight.
Next, this quartz glass plate was placed in a 1 liter Tedlar bag, and then air containing isopropanol (IPA) vapor was circulated in the bag for 1 hour to saturate the gas adsorption of titanium dioxide fine particles.
With this state as the state before irradiation with visible light, the concentrations of IPA and acetone in the bag were measured by gas chromatography. As a result, IPA was 1500 ppm and acetone was not detected (ND).
The Tedlar bag was irradiated for 5 hours at a wavelength of 420 nm and an intensity of 0.5 mW / cm 2 with a fluorescent lamp provided with a cover for cutting out ultraviolet light having a wavelength shorter than 410 nm. Every 30 minutes from the start of irradiation, the IPA concentration and the concentration of acetone produced by the oxidation of IPA were measured.
The results are shown in Table 1.
［実施例２］
窒素３０００ｐｐｍおよび炭素７５ｐｐｍをドープした二酸化チタン微粒子（短径約１０ｎｍ、長径約３０ｎｍの長球状の一次粒子）を合成した。
この二酸化チタン微粒子について、実施例１と同様にして、可視光に対する光触媒活性を評価した。
この結果を表１に示す。
[Example 2]
Titanium dioxide fine particles doped with 3000 ppm nitrogen and 75 ppm carbon (primary spherical particles having a minor axis of about 10 nm and a major axis of about 30 nm) were synthesized.
About this titanium dioxide fine particle, it carried out similarly to Example 1, and evaluated the photocatalytic activity with respect to visible light.
The results are shown in Table 1.
［実施例３］
窒素３０００ｐｐｍおよび炭素７．５ｐｐｍをドープした二酸化チタン微粒子（短径約１０ｎｍ、長径約３０ｎｍの長球状の一次粒子）を合成した。
この二酸化チタン微粒子について、実施例１と同様にして、可視光に対する光触媒活性を評価した。
この結果を表１に示す。
[Example 3]
Titanium dioxide fine particles doped with 3000 ppm nitrogen and 7.5 ppm carbon (primary spherical particles having a minor axis of about 10 nm and a major axis of about 30 nm) were synthesized.
About this titanium dioxide fine particle, it carried out similarly to Example 1, and evaluated the photocatalytic activity with respect to visible light.
The results are shown in Table 1.
［比較例１］
窒素３０００ｐｐｍをドープした二酸化チタン微粒子（一次粒径約５〜３０ｎｍ）を合成した。
この二酸化チタン微粒子について、実施例１と同様にして、可視光に対する光触媒活性を評価した。
この結果を表１に示す。
[Comparative Example 1]
Titanium dioxide fine particles (primary particle size of about 5 to 30 nm) doped with 3000 ppm of nitrogen were synthesized.
About this titanium dioxide fine particle, it carried out similarly to Example 1, and evaluated the photocatalytic activity with respect to visible light.
The results are shown in Table 1.
［比較例２］
市販の酸素欠乏型二酸化チタン微粒子（Ａ社製）について、実施例１と同様にして、可視光に対する光触媒活性を評価した。
この結果を表１に示す。
[Comparative Example 2]
The commercially available oxygen-deficient titanium dioxide fine particles (manufactured by Company A) were evaluated in the same manner as in Example 1 for photocatalytic activity with respect to visible light.
The results are shown in Table 1.
［比較例３］
従来の窒素ドープ型二酸化チタン微粒子（Ｂ社製）（一次粒径５〜１０ｎｍ）について、実施例１と同様にして、可視光に対する光触媒活性を評価した。
この結果を表１に示す。
[Comparative Example 3]
For conventional nitrogen-doped titanium dioxide fine particles (manufactured by B company) (primary particle size 5 to 10 nm), the photocatalytic activity for visible light was evaluated in the same manner as in Example 1.
The results are shown in Table 1.
表１に示した評価結果から、窒素および炭素の２種類のアニオンをドープした二酸化チタン微粒子（実施例１〜３）は、可視光の照射によって、ＩＰＡの酸化反応により生成したアセトンが検出され、可視光に対する光触媒活性を示すことが認められた。
また、これらの実施例１〜３の二酸化チタン微粒子は、同じ照射時間でのアセトンの生成量から、窒素のみをドープした場合（比較例１）または酸素欠乏欠陥型の市販品（比較例２）よりも、優れた光触媒活性を示し、特に、実施例１は、比較例１および２と比べて、２倍以上のＩＰＡ酸化活性を示すことが認められた。
From the evaluation results shown in Table 1, titanium dioxide fine particles (Examples 1 to 3) doped with two types of anions, nitrogen and carbon, detected by acetone irradiation generated by the oxidation reaction of IPA, It was found to exhibit photocatalytic activity for visible light.
In addition, these titanium dioxide fine particles of Examples 1 to 3 were doped with only nitrogen (Comparative Example 1) or an oxygen-deficient defect type commercial product (Comparative Example 2) from the amount of acetone produced at the same irradiation time. In particular, it was confirmed that the photocatalytic activity superior to that of Example 1 was exhibited, and in particular, Example 1 exhibited an IPA oxidation activity twice or more that of Comparative Examples 1 and 2.
なお、実施例２、３および比較例３の二酸化チタン微粒子を、それぞれ、１８０℃で１時間石英ガラス板上に焼き付けた試料について、上記と同様の可視光活性評価試験を行ったところ、実施例２、３については、約７５％のＩＰＡ分解効果が認められたが、比較例３については、ＩＰＡ分解効果は約５０％にまで低下した。
このことから、実施例２、３に係る二酸化チタン粒子は、比較例３に比べて、高温処理した場合においても、可視光に対する光触媒活性が優れていることが認められた。
なお、光を照射しない暗い状態のままでは、いずれの二酸化チタン粒子も、変化は観察されなかった。
In addition, when the titanium dioxide fine particles of Examples 2 and 3 and Comparative Example 3 were each baked on a quartz glass plate at 180 ° C. for 1 hour, a visible light activity evaluation test similar to the above was performed. About 2 and 3, the IPA decomposition effect of about 75% was recognized, but about the comparative example 3, the IPA decomposition effect fell to about 50%.
From this, it was recognized that the titanium dioxide particles according to Examples 2 and 3 were superior in photocatalytic activity to visible light even when treated at a high temperature as compared with Comparative Example 3.
Note that no change was observed in any of the titanium dioxide particles in a dark state where no light was irradiated.
また、上記実施例１および比較例３の二酸化チタン微粒子について、ＫＢｒ法によるフーリエ変換赤外吸収スペクトル（ＦＴ−ＩＲ）を測定した。
装置は、Ｂｒｕｋｅｒ製ＩＦＳ１１３Ｖ型および日立製作所製２６０−５０型フーリエ変換赤外分光光度計を使用し、分解能は４ｃｍ-1で測定した。
測定試料は、乳鉢でＫＢｒと混合し、粉末状とした後、錠剤成型器でペレット状にしたものを用いた。
測定されたスペクトルを図６および図７に示す。
Moreover, the Fourier-transform infrared absorption spectrum (FT-IR) by KBr method was measured about the titanium dioxide fine particle of the said Example 1 and the comparative example 3. FIG.
The apparatus used was a Bruker IFS113V type and a Hitachi 260-50 type Fourier transform infrared spectrophotometer, and the resolution was measured at 4 cm −1 .
The measurement sample was mixed with KBr in a mortar to form a powder and then pelletized with a tablet molding machine.
The measured spectrum is shown in FIG. 6 and FIG.
図６および図７に示したように、ＦＴ−ＩＲの測定結果は、実施例１では、波数５８０ｃｍ-1および３４０ｃｍ-1において吸収ピークがあり、窒素のみがドープされた比較例３とはそのピーク位置は異なることが認められた。
前記吸収ピークは、ドープされた炭素および窒素に基づくものであり、本発明に係る二酸化チタン微粒子において特徴的なものである。
As shown in FIGS. 6 and 7, the measurement results FT-IR, in the first embodiment, there is an absorption peak at a
The absorption peak is based on doped carbon and nitrogen, and is characteristic in the titanium dioxide fine particles according to the present invention.
［実施例４］
平均粒径６ｎｍのほぼ球状の二酸化チタン原料微粒子５０ｇを耐火性トレーに載置し、ＮＨ3ガスおよびプロパンガスの混合ガス雰囲気下、５７０℃で２時間熱処理して、二酸化チタン微粒子を作製した。
このとき、プロパンガスのＮＨ3ガスに対する濃度を変化させて、プロパンガスの各濃度における光触媒活性を評価した。これらの結果を、図１にグラフとして示す。
なお、上記光触媒活性の評価は、実施例１と同様の可視光活性評価試験（１時間照射）により行った。
[Example 4]
50 g of substantially spherical titanium dioxide raw material fine particles having an average particle diameter of 6 nm were placed on a refractory tray and heat-treated at 570 ° C. for 2 hours in a mixed gas atmosphere of NH 3 gas and propane gas to produce titanium dioxide fine particles.
At this time, the photocatalytic activity at each concentration of propane gas was evaluated by changing the concentration of propane gas with respect to NH 3 gas. These results are shown as a graph in FIG.
The photocatalytic activity was evaluated by the same visible light activity evaluation test (1 hour irradiation) as in Example 1.
図１のグラフに示したように、プロパンガスがＮＨ3ガスに対して、０％の場合は、可視光照射に対する光触媒活性はやや劣り、２％以上においては、十分な効果が認められた。さらに、５％以上の場合には、ほぼ一定して、優れた光触媒活性が認められた。
なお、得られた二酸化チタン微粒子は、いずれも、長径が約４０ｎｍの長球状に成長しており、黄色みを帯びた粒子であった。
As shown in the graph of FIG. 1, when the propane gas was 0% with respect to the NH 3 gas, the photocatalytic activity with respect to visible light irradiation was slightly inferior, and when it was 2% or more, a sufficient effect was observed. Furthermore, in the case of 5% or more, excellent photocatalytic activity was recognized almost constant.
In addition, all of the obtained titanium dioxide fine particles grew into an oblong shape having a major axis of about 40 nm, and were yellowish particles.
［実施例５］
平均粒径６ｎｍのほぼ球状の二酸化チタン原料微粒子５０ｇを耐火性トレーに載置し、ＮＨ3ガスおよびプロパンガス（ＮＨ3ガスに対して５％）の混合ガス雰囲気下、５００〜６３０℃の範囲における各温度で２時間熱処理して、二酸化チタン微粒子を作製した。
そして、各熱処理温度における光触媒活性を評価した。これらの結果を、図２にグラフとして示す。
なお、上記光触媒活性の評価は、実施例１と同様の可視光活性評価試験（１時間照射）により行った。
[Example 5]
50 g of substantially spherical titanium dioxide raw material fine particles having an average particle diameter of 6 nm are placed on a refractory tray, and a mixed gas atmosphere of NH 3 gas and propane gas (5% with respect to NH 3 gas) is in a range of 500 to 630 ° C. The titanium dioxide fine particles were produced by heat treatment at each temperature for 2 hours.
And the photocatalytic activity in each heat processing temperature was evaluated. These results are shown as a graph in FIG.
The photocatalytic activity was evaluated by the same visible light activity evaluation test (1 hour irradiation) as in Example 1.
図２のグラフに示したように、熱処理温度が５００℃以上６２０℃以下の場合、優れた可視光照射に対する光触媒活性が認められ、特に、５３０℃以上５９０℃以下の場合に、その効果の向上が顕著であった。
なお、５７０℃で熱処理して得られた二酸化チタン微粒子について分析したところ、Ｎが３５００ｗｔｐｐｍ、Ｃが１６０ｗｔｐｐｍ含まれていた。
As shown in the graph of FIG. 2, when the heat treatment temperature is 500 ° C. or more and 620 ° C. or less, excellent photocatalytic activity for visible light irradiation is recognized, and particularly when the heat treatment temperature is 530 ° C. or more and 590 ° C. or less, the effect is improved. Was remarkable.
When titanium dioxide fine particles obtained by heat treatment at 570 ° C. were analyzed, N was contained in 3500 wtppm and C was contained in 160 wtppm.
また、得られた二酸化チタン微粒子は、いずれも、長径が約３０〜４０ｎｍの長球状に成長しており、黄色みを帯びた粒子であった。
図３〜５に、５００℃、５７０℃、６２０℃の各温度で熱処理して得られた二酸化チタン微粒子のＦＥ‐ＳＥＭ写真を示す。
Moreover, all the obtained titanium dioxide fine particles were grown in an oblong shape having a major axis of about 30 to 40 nm, and were yellowish particles.
3 to 5 show FE-SEM photographs of titanium dioxide fine particles obtained by heat treatment at temperatures of 500 ° C., 570 ° C., and 620 ° C. FIG.
［実施例６］
実施例１の二酸化チタン微粒子を水に分散させて（固形分５％）、これを２７ｃｍ×９０ｃｍの障子紙に塗布し、室温乾燥させ、これを試験試料として、下記に示すようなホルムアルデヒド分解能評価を行った。
前記試験試料を容積１ｍ3のＳＵＳ製ボックスに入れた後、ホルムアルデヒドを１．５ｐｐｍ導入し、蛍光灯（Ｔｏｓｈｉｂａ ＦＬＲ２０ｗ，Ｗ／Ｍ）から１０ｃｍの位置にセットした。
蛍光灯照射時のホルムアルデヒド濃度をマルチガスモニタ（Ｉｎｎｏｖａ １３１２型）で測定した。
この測定結果を図８に示す。
[Example 6]
The titanium dioxide fine particles of Example 1 were dispersed in water (5% solid content), applied to 27 cm × 90 cm shoji paper, dried at room temperature, and this was used as a test sample to evaluate formaldehyde resolution as shown below. Went.
The test sample was placed in a SUS box having a volume of 1 m 3 , 1.5 ppm of formaldehyde was introduced, and the test sample was set at a
The formaldehyde concentration at the time of fluorescent lamp irradiation was measured with a multi-gas monitor (Innova 1312 type).
The measurement results are shown in FIG.
［比較例４］
比較例２の二酸化チタン微粒子について、実施例６と同様にして、ホルムアルデヒド分解能評価を行った。
この測定結果を図８に示す。
[Comparative Example 4]
The titanium dioxide fine particles of Comparative Example 2 were evaluated for formaldehyde resolution in the same manner as in Example 6.
The measurement results are shown in FIG.
図８に示したように、実施例６は、比較例４に比べて、蛍光灯照射による優れたアルデヒド分解能を有することが認められた。
このことからも、本発明に係る二酸化チタン微粒子は、屋内の蛍光灯照射による消臭作用等の応用用途が期待される。
As shown in FIG. 8, Example 6 was found to have superior aldehyde resolution by fluorescent lamp irradiation as compared with Comparative Example 4.
Also from this, the titanium dioxide fine particles according to the present invention are expected to be used for applications such as deodorizing by indoor fluorescent lamp irradiation.
Claims (12)
二酸化チタン原料微粒子を、Ｎ含有ガスを含む還元性ガス雰囲気下、５００℃以上６２０℃以下で熱処理することにより得ることを特徴とする二酸化チタン微粒子の製造方法。 A method for producing the titanium dioxide particles according to any one of claims 1 to 8,
A method for producing titanium dioxide fine particles, characterized by being obtained by heat-treating titanium dioxide raw material fine particles at 500 ° C. or more and 620 ° C. or less in a reducing gas atmosphere containing N-containing gas.
二酸化チタン原料微粒子を、Ｎ、ＣおよびＨを含むガス雰囲気下、５００℃以上６２０℃以下で熱処理することにより得ることを特徴とする二酸化チタン微粒子の製造方法。 A method for producing the titanium dioxide fine particles according to any one of claims 1 to 8,
A method for producing titanium dioxide fine particles, which is obtained by heat-treating titanium dioxide raw material fine particles at a temperature of 500 ° C. or higher and 620 ° C. or lower in a gas atmosphere containing N, C and H.
二酸化チタン原料微粒子を、ＮＨ3ガスおよびＣを含むガス雰囲気下、５００℃以上６２０℃以下で熱処理することにより得ることを特徴とする二酸化チタン微粒子の製造方法。 A method for producing the titanium dioxide fine particles according to any one of claims 1 to 8,
A method for producing titanium dioxide fine particles, which is obtained by heat-treating titanium dioxide raw material fine particles at 500 ° C. or more and 620 ° C. or less in a gas atmosphere containing NH 3 gas and C.
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