JP3933640B2 - photocatalyst - Google Patents
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- JP3933640B2 JP3933640B2 JP2004099937A JP2004099937A JP3933640B2 JP 3933640 B2 JP3933640 B2 JP 3933640B2 JP 2004099937 A JP2004099937 A JP 2004099937A JP 2004099937 A JP2004099937 A JP 2004099937A JP 3933640 B2 JP3933640 B2 JP 3933640B2
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- 239000011941 photocatalyst Substances 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910005438 FeTi Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- -1 superoxide anions Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Description
本発明は、酸化亜鉛、酸化チタン及び酸化鉄の複合酸化物よりなる光触媒に関するものである。 The present invention relates to a photocatalyst comprising a composite oxide of zinc oxide, titanium oxide and iron oxide.
酸化チタンの光触媒活性は周知である。また、この酸化チタンの光触媒特性は紫外光領域（波長約３８０ｎｍ以下）で発揮されるため、可視光領域でも光触媒特性が発現するための研究も種々なされている（例えば特開平９−２６２４８２号公報、特開２００１−２０５１０３号公報、特許第３２１５６９８号）。
特開平９−２６２４８２号では、触媒活性の高いアナターゼ型ＴｉＯ２にＣｒ，Ｖ等の金属元素をイオン注入して可視光での動作を可能にしているが、イオン注入には装置が大規模になり高価であるという問題点がある。 In Japanese Patent Laid-Open No. 9-262482, a metal element such as Cr or V is ion-implanted into anatase-type TiO 2 having high catalytic activity to enable operation with visible light. There is a problem that it is expensive.
特許第３２１５６９８号ではＴｉＯ２の酸素に欠損を作ることにより、また、特開２００１−２０５１０３号では酸素の一部を窒素や硫黄で置換することにより、それぞれ可視光での動作を可能にしているが、多くの酸素欠損を形成しているため、不安定な結晶構造をとりやすく光触媒作用を長期間にわたって持続させることは難しい。 In Japanese Patent No. 3215698, a deficiency is formed in oxygen of TiO 2 , and in Japanese Patent Laid-Open No. 2001-205103, a part of oxygen is replaced with nitrogen or sulfur to enable operation with visible light. However, since many oxygen vacancies are formed, it is easy to form an unstable crystal structure, and it is difficult to maintain the photocatalytic action over a long period of time.
本発明は、可視光下での光触媒作用を長期間にわたって発揮する光触媒を提供することを目的とする。 An object of this invention is to provide the photocatalyst which exhibits the photocatalytic action under visible light over a long period of time.
本発明（請求項１）の光触媒は、Ｚｎ１＋０．５ｘＦｅ２−ｘＴｉ０．５ｘＯ４（０．５≦ｘ≦２）で表される複合酸化物よりなることを特徴とするものである。 The photocatalyst of the present invention (Claim 1) is composed of a composite oxide represented by Zn 1 + 0.5x Fe 2-x Ti 0.5x O 4 ( 0.5 ≦ x ≦ 2). is there.
請求項２の光触媒は、請求項１において、ｘが０．５〜１．５であることを特徴とするものである。The photocatalyst according to claim 2 is characterized in that, in claim 1, x is 0.5 to 1.5.
請求項３の光触媒は、請求項１において、ｘが０．７〜１．３であることを特徴とするものである。 The photocatalyst according to claim 3 is the photocatalyst according to claim 1, wherein x is 0.7 to 1.3.
請求項４の光触媒は、請求項１ないし３のいずれか１項において、上記組成範囲の共沈殿物の少なくとも一部を結晶化させることにより製造されたものであることを特徴とするものである。 The photocatalyst according to claim 4 is the one according to any one of claims 1 to 3 , wherein the photocatalyst is produced by crystallizing at least a part of the coprecipitate in the composition range. .
本発明の光触媒も含めて、一般に光触媒は、半導体バンドギャップ以上のエネルギーを吸収すると、電子と正孔を生成しこれらがそれぞれ還元反応、酸化反応を行う。この生成した電子や正孔に、水や酸素などが反応することによってヒドロキシラジカルやスーパーオキサイドアニオン等の活性酸素が生成し、これら活性酸素がＶＯＣ、悪臭ガスなどの分解を行う。種々の研究の結果、本発明の光触媒は、可視光下において上記の光触媒作用を発揮することが認められた。本発明の光触媒は、その組成に特徴を有するものであり、酸素欠損ではなくこの組成を有する複合酸化物によって光触媒作用を発揮するため、経時的な特性低下がなく、長期にわたり、可視光下でも十分な光触媒作用を発揮する。 In general, including the photocatalyst of the present invention, when the photocatalyst absorbs energy exceeding the semiconductor band gap, it generates electrons and holes, which respectively undergo a reduction reaction and an oxidation reaction. The generated electrons and holes react with water, oxygen, and the like to generate active oxygen such as hydroxy radicals and superoxide anions, and these active oxygen decomposes VOC, malodorous gas, and the like. As a result of various studies, it was confirmed that the photocatalyst of the present invention exerts the above-described photocatalytic action under visible light. The photocatalyst of the present invention is characterized by its composition, and exhibits a photocatalytic action by a composite oxide having this composition rather than oxygen vacancies. Exhibits sufficient photocatalytic activity.
なお、本発明の光触媒は、上記組成範囲の共沈物の少なくとも一部を結晶化させることにより製造されたものが好ましく、これにより、比表面積の大きな光触媒が得られるため重量あたりの性能が非常に優れたものとなる。また、１００℃付近からの低温合成が可能であるため、低エネルギー、低コストで合成することができる。 The photocatalyst of the present invention is preferably produced by crystallizing at least a part of the coprecipitate having the above composition range, and thus a photocatalyst having a large specific surface area can be obtained, so that the performance per weight is extremely high. It will be excellent. Moreover, since low temperature synthesis is possible from around 100 ° C., synthesis can be performed with low energy and low cost.
本発明の光触媒を構成する複合酸化物の組成は、前記の通り、Ｚｎ１＋０．５ｘＦｅ２−ｘＴｉ０．５ｘＯ４（０．５≦ｘ≦２）で表わされる。種々の実験の結果、ｘ＝０．５のＺｎ １．２５ Ｆｅ １．５ Ｔｉ ０．２５ Ｏ ４ からｘ＝２のＺｎ２ＴｉＯ４の全域において、可視光下でも十分な光触媒作用が奏されることが認められたが、中でもｘが０．７〜１．３特に０．８〜１．２とりわけ約１である場合に著しく優れた光触媒作用が奏されることが認められた。 As described above, the composition of the complex oxide constituting the photocatalyst of the present invention is represented by Zn 1 + 0.5x Fe 2-x Ti 0.5x O 4 ( 0.5 ≦ x ≦ 2). As a result of various experiments, a sufficient photocatalytic effect is exhibited even under visible light in the entire region from Zn = 1.25 Fe 1.5 Ti 0.25 O 4 with x = 0.5 to Zn 2 TiO 4 with x = 2. However, it was found that a particularly excellent photocatalytic effect was exhibited when x was 0.7 to 1.3, particularly 0.8 to 1.2, especially about 1.
本発明の光触媒を製造するには、ＴｉＯ２、ＺｎＯ及びＦｅＯを目的とする割合にて混合・粉砕し、必要に応じ成形した後、焼成すればよい。 In order to produce the photocatalyst of the present invention, TiO 2 , ZnO and FeO may be mixed and pulverized at a desired ratio, formed as necessary, and then fired.
特に本発明を限定するものではないが、混合、粉砕はエタノール等の溶媒を用いて湿式方式にて行うのが好適である。また、混合、粉砕後は、プレス成形し、その後の焼成工程での焼結を促進するのが好適である。焼成雰囲気は大気が好適であり、焼成温度は１１００〜１２５０℃程度が好適である。 Although the present invention is not particularly limited, mixing and pulverization are preferably performed by a wet method using a solvent such as ethanol. Further, after mixing and pulverization, it is preferable to press-mold and promote sintering in the subsequent firing step. The firing atmosphere is preferably air, and the firing temperature is preferably about 1100 to 1250 ° C.
焼成後は、そのまま光触媒として用いてもよく、粉砕して光触媒粉体又は粒体として用いてもよい。 After firing, it may be used as it is as a photocatalyst, or may be pulverized and used as a photocatalyst powder or granules.
本発明の光触媒は、上記組成の複合酸化物よりなるものであるが、光触媒作用を損なわない限り、他の金属酸化物や金属成分を含んでもよい。また、光触媒の焼結体ないし粒子の表面に金属や金属酸化物のコーティングや担持処理が施されていてもよい。 The photocatalyst of the present invention comprises a composite oxide having the above composition, but may contain other metal oxides and metal components as long as the photocatalytic action is not impaired. Further, the surface of the sintered body or particles of the photocatalyst may be subjected to a coating or supporting treatment with a metal or metal oxide.
なお、焼結体及び共沈殿物を熟成したものの結晶構造はｘ＝０．５〜２のいずれにおいても、スピネル構造を有する単結晶又は固溶体である。 In addition, the crystal structure of what aged the sintered compact and the coprecipitate is a single crystal or a solid solution having a spinel structure in any of x = 0.5-2 .
以下、実施例及び比較例について説明する。 Hereinafter, examples and comparative examples will be described.
実施例１〜４及び参考例１
Ｚｎ１＋０．５ｘＦｅ２−ｘＴｉ０．５ｘＯ４において、ｘ＝０（参考例１）、０．５、１．０、１．５、２．０（実施例１〜４）としたＺｎＦｅ２Ｏ４、Ｚｎ１．２５Ｆｅ１．５Ｔｉ０．２５Ｏ４、Ｚｎ１．５ＦｅＴｉ０．５Ｏ４、Ｚｎ１．７５Ｆｅ０．５Ｔｉ０．７５Ｏ４及びＺｎ２ＴｉＯ４をそれぞれ次のようにして製造した。即ち、試薬特級のＺｎＯ、ＴｉＯ２及びＦｅ２Ｏ３を上記比率となるように秤量し、エタノール中で混練し、乾燥後プレスによりペレットを作成した。これを空気中蒸気圧下で電気炉で１２００℃、２４時間焼成した。焼成終了後、乳鉢で粉砕しサンプルとした。
Examples 1 to 4 and Reference Example 1
Zn 1 + 0.5x Fe 2-x Ti 0.5x O 4 ZnFe with x = 0 (Reference Example 1) , 0.5, 1.0, 1.5, 2.0 (Examples 1 to 4) 2 O 4 , Zn 1.25 Fe 1.5 Ti 0.25 O 4 , Zn 1.5 FeTi 0.5 O 4 , Zn 1.75 Fe 0.5 Ti 0.75 O 4 and Zn 2 TiO 4 . Each was manufactured as follows. That is, reagent-grade ZnO, TiO 2 and Fe 2 O 3 were weighed so as to have the above ratio, kneaded in ethanol, dried, and pressed to form pellets. This was fired at 1200 ° C. for 24 hours in an electric furnace under vapor pressure in the air. After firing, the sample was pulverized in a mortar.
各サンプルについて紫外可視吸収スペクトルの測定を行った結果、４００ｎｍ以上の可視光の吸収が確認された。 As a result of measuring the ultraviolet-visible absorption spectrum for each sample, absorption of visible light of 400 nm or more was confirmed.
また、各サンプルの触媒活性について次のようにして評価した。即ち、各サンプル０．５ｇをそれぞれガラス板に付着させた。各ガラス板をそれぞれアセトアルデヒド濃度５００ｐｐｍの３リットルの密閉容器内中に配置した。このとき、密閉容器は遮光された状態とし、アセトアルデヒド濃度５００ｐｐｍで吸着飽和するまでガス交換を行った。吸着飽和に達した後、蛍光灯（２０Ｗ）の波長４００ｎｍ未満の光をカットし、４００ｎｍ以上の光のみを該ガラス板に２４時間照射し、容器中のアセトアルデヒド濃度を測定し、アセトアルデヒドの除去率を測定した。除去率はサンプル比表面積当たりの数値で示した。 Further, the catalytic activity of each sample was evaluated as follows. That is, 0.5 g of each sample was adhered to the glass plate. Each glass plate was placed in a 3 liter sealed container with an acetaldehyde concentration of 500 ppm. At this time, the sealed container was shielded from light, and gas exchange was performed until adsorption saturation occurred at an acetaldehyde concentration of 500 ppm. After reaching adsorption saturation, the light with a wavelength of less than 400 nm of a fluorescent lamp (20 W) is cut, only the light of 400 nm or more is irradiated onto the glass plate for 24 hours, the acetaldehyde concentration in the container is measured, and the acetaldehyde removal rate Was measured. The removal rate was shown as a numerical value per sample specific surface area.
なお、参考のために、市販の酸化チタン系光触媒についても同様の評価を行った。結果は次の通りである。 For reference, the same evaluation was performed for a commercially available titanium oxide photocatalyst. The results are as follows.
比較例１〜４
下記組成となるように原料調合を行った他は同様にして製造したＺｎＯ−ＴｉＯ２−ＦｅＯ系複合酸化物粉体について、上記と同一のアセトアルデヒド除去性能評価を行った。結果は次の通りである。
Comparative Examples 1-4
The same acetaldehyde removal performance evaluation as described above was performed on the ZnO—TiO 2 —FeO-based composite oxide powder produced in the same manner except that the raw materials were prepared to have the following composition. The results are as follows.
なお、この比較例１〜４の組成と、Ｚｎ１＋０．５ｘＦｅ２−ｘＴｉ０．５ｘＯ４（０≦ｘ≦２）の組成とをＺｎＯ−ＴｉＯ２−ＦｅＯ三元組成図（図１）に示す。 The composition of Comparative Examples 1 to 4 and the composition of Zn 1 + 0.5x Fe 2-x Ti 0.5x O 4 (0 ≦ x ≦ 2) are represented by a ZnO—TiO 2 —FeO ternary composition diagram (FIG. 1). ).
実施例５
Ｚｎ１＋０．５ｘＦｅ２−ｘＴｉ０．５ｘＯ４において、ｘ＝１．０としたＺｎ１．５Ｆｅ２Ｔｉ０．５Ｏ４を次のようにして製造した。即ち、試薬特級のＺｎＳＯ４・７Ｈ２Ｏ、Ｔｉ（ＳＯ４）２溶液及びＦｅＳＯ４・７Ｈ２Ｏを上記比率となるように秤量し、１ｍｏｌ／ｌ水溶液に調製した後、混合した。この溶液を０．０３ｍｏｌ／ｌＮａＯＨ水溶液中に滴下し沈殿物を製造した。このとき溶液量は１：１００とした。製造した沈殿物を蒸留水で水洗した後、蒸留水中に分散し、ｐＨを約８．５に調製したものを１００℃、１２時間熟成した。熟成後、沈殿物を水洗し１００℃で乾燥した。焼成終了後、乳鉢で粉砕しサンプルとした。上記と同一のアセトアルデヒド除去性能評価を行った。結果は次の通りである。
Example 5
In Zn 1 + 0.5x Fe 2-x Ti 0.5x O 4 , Zn 1.5 Fe 2 Ti 0.5 O 4 with x = 1.0 was produced as follows. That is, reagent-grade ZnSO 4 · 7H 2 O, Ti (SO 4 ) 2 solution and FeSO 4 · 7H 2 O were weighed so as to have the above ratios, prepared to a 1 mol / l aqueous solution, and then mixed. This solution was dropped into a 0.03 mol / l NaOH aqueous solution to produce a precipitate. At this time, the amount of the solution was 1: 100. The produced precipitate was washed with distilled water, then dispersed in distilled water, and a pH adjusted to about 8.5 was aged at 100 ° C. for 12 hours. After aging, the precipitate was washed with water and dried at 100 ° C. After firing, the sample was pulverized in a mortar. The same acetaldehyde removal performance evaluation as above was performed. The results are as follows.
以上の実施例と比較例の実験結果から明らかな通り、本発明の光触媒は、可視光下での光触媒特性に優れる。 As is clear from the experimental results of the above examples and comparative examples, the photocatalyst of the present invention is excellent in photocatalytic properties under visible light.
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| CN100357021C (en) * | 2006-06-06 | 2007-12-26 | 北京科技大学 | Process of preparing photocatalyst material with concentrated ilmenite |
| JP5036443B2 (en) * | 2007-07-31 | 2012-09-26 | 国立大学法人 東京大学 | Photocatalytic material |
| JP2010046604A (en) * | 2008-08-21 | 2010-03-04 | Utsunomiya Univ | Photocatalyst, method for producing hydrogen and method for decomposing organic matter |
| JP5360817B2 (en) * | 2009-05-28 | 2013-12-04 | 独立行政法人産業技術総合研究所 | Visible light responsive composition and photoelectrode, photocatalyst, and photosensor using the same |
| JP2015059049A (en) * | 2013-09-17 | 2015-03-30 | 株式会社豊田中央研究所 | Semiconductor material, photo-electrode material, photocatalyst material, and method of producing semiconductor material |
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