JP2001096154A - Vanadium oxide/titania hybrid photocatalyst and its manufacturing method - Google Patents
Vanadium oxide/titania hybrid photocatalyst and its manufacturing methodInfo
- Publication number
- JP2001096154A JP2001096154A JP27652199A JP27652199A JP2001096154A JP 2001096154 A JP2001096154 A JP 2001096154A JP 27652199 A JP27652199 A JP 27652199A JP 27652199 A JP27652199 A JP 27652199A JP 2001096154 A JP2001096154 A JP 2001096154A
- Authority
- JP
- Japan
- Prior art keywords
- titania
- vanadium oxide
- thin film
- vanadium
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 283
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 82
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000010409 thin film Substances 0.000 claims abstract description 49
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 19
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000006104 solid solution Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 13
- -1 titanium alkoxide Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 229920000592 inorganic polymer Polymers 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 229910010413 TiO 2 Inorganic materials 0.000 description 21
- 230000007613 environmental effect Effects 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000011324 bead Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101000741917 Homo sapiens Serine/threonine-protein phosphatase 1 regulatory subunit 10 Proteins 0.000 description 1
- 229920002201 Oxidized cellulose Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 102100038743 Serine/threonine-protein phosphatase 1 regulatory subunit 10 Human genes 0.000 description 1
- 150000001298 alcohols Chemical class 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229940107304 oxidized cellulose Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【０００１】本発明は、エネルギーミニマム型環境浄化
システム用の光触媒モジュールなどの開発の目的で、高
効率に環境汚染物質を分解できる光触媒に関し、チタニ
アにバナジウム酸化物を固溶させることにより、チタニ
アより高効率での環境汚染物質の分解を可能としたバナ
ジウム酸化物／チタニアハイブリッド光触媒に関する。[0001] The present invention relates to a photocatalyst capable of decomposing environmental pollutants with high efficiency for the purpose of developing a photocatalyst module for an energy minimum type environmental purification system, and the like. The present invention relates to a vanadium oxide / titania hybrid photocatalyst capable of decomposing environmental pollutants with high efficiency.
【０００２】[0002]
【従来の技術】光触媒は、太陽光を利用し環境汚染物質
を分解除去できるため、エネルギーミニマム型環境浄化
材料として期待されている。これまで、大気や水などを
対象とした環境浄化材料としての光触媒は種々検討され
ているが、化学的安定性や安全性の観点からチタニアに
優るものはないとされ、これについて環境浄化材料への
応用が活発に検討されている。しかし、優れた性能のチ
タニアはいずれも微粉末であり、取扱いが困難であるば
かりか、環境浄化システムとして使用するためには、気
相では流動層で、水系では懸濁させて使用するため、装
置が大掛かりになったり、触媒の回収が困難である。こ
れを解決するために基材に固定化して用いられている
が、一般的に困難であり、実用的な固定化としてはフッ
素樹脂やコンクリートに練りこむ方法と塗料があるにす
ぎず、その場合には性能の低下がまぬがれないという欠
点があった。2. Description of the Related Art Photocatalysts are expected to be energy-minimum type environmental purification materials because they can decompose and remove environmental pollutants using sunlight. A variety of photocatalysts have been studied as environmental purification materials for air and water, but none of them are superior to titania in terms of chemical stability and safety. The application of is being actively studied. However, titania with excellent performance is a fine powder, which is difficult to handle.In addition, in order to use it as an environmental purification system, it is used as a fluidized bed in the gas phase and suspended in an aqueous system. The equipment becomes large-scale and it is difficult to recover the catalyst. In order to solve this, it is used by immobilizing on the base material, but it is generally difficult, and as a practical immobilization, there is only a method and a paint kneaded in a fluororesin or concrete, in which case Has a drawback that the performance cannot be reduced.
【０００３】一方、性能の向上を目指した研究も多く行
われ、チタニアに白金、パラジウム、ロジウムなどを担
持して光触媒中の酸化・還元サイトを分離する試みや、
イオン注入法でクロムやバナジウム原子を打ち込み、可
視光を利用する試みが行われている。しかし、これらの
方法は高価な貴金属を使用したり、特殊な装置を必要と
することから大量製造には不向きであり環境浄化システ
ムを考えると実用性に乏しい。On the other hand, there have been many studies aimed at improving the performance. Attempts have been made to separate oxidation / reduction sites in a photocatalyst by supporting platinum, palladium, rhodium, etc. on titania,
Attempts have been made to use visible light by implanting chromium and vanadium atoms by ion implantation. However, these methods use expensive precious metals and require special equipment, so they are not suitable for mass production and are not practical in consideration of an environmental purification system.
【０００４】また、酸化物イオンをドープしたチタニア
やバナジウム酸化物の光触媒活性がチタニアと比較され
ているが、検討された光触媒活性は水の分解効率、有機
化合物の異性化、可視光の利用率などであり、環境汚染
物質の分解除去高率でチタニアに優る結果は得られてい
ない。The photocatalytic activity of titania or vanadium oxide doped with oxide ions has been compared with that of titania. The photocatalytic activities studied include water decomposition efficiency, isomerization of organic compounds, and utilization of visible light. Thus, a result that is superior to titania at a high rate of decomposition and removal of environmental pollutants has not been obtained.
【０００５】[0005]
【発明が解決しようとしている課題】環境浄化材料とし
て最も優れた性能を有するチタニアでも、３８０ｎｍ以
下の波長の紫外線を光反応に利用している。これは全太
陽光エネルギーの４％にすぎず、本来低濃度の汚染物質
を分解除去することしかできない。したがって、実用的
なエネルギーミニマム型環境浄化システムに使用する光
触媒に求められる特性としては、第一に、できるだけ高
効率に汚染物質を分解除去できシステムが小型化できる
こと、第二に、化学的安定性や安全性、第三に、取扱い
が容易であることが要求される。The titania which has the best performance as an environmental purification material also utilizes ultraviolet light having a wavelength of 380 nm or less for photoreaction. This is only 4% of the total solar energy and can only decompose and remove low concentrations of pollutants. Therefore, the characteristics required of a photocatalyst used in a practical energy minimum type environmental purification system include: first, the ability to decompose and remove pollutants with the highest possible efficiency and reduce the size of the system; and secondly, chemical stability. Third, it must be easy to handle.
【０００６】しかしながら、従来のチタニアは、化学的
安定性や安全性は十分な性能を有しているものの、取扱
いが容易で、しかも、高効率に汚染物質を分解除去でき
るとは言えない。[0006] However, conventional titania has sufficient chemical stability and safety properties, but cannot be said to be easy to handle and capable of decomposing and removing pollutants with high efficiency.
【０００７】そこで本発明は、前記チタニアにおける課
題と前記のエネルギーミニマム型環境浄化システムに求
められる特性に鑑み、チタニアより高効率に汚染物質を
分解除去でき、化学的安定性や安全性に優れ、取扱いが
容易で、しかも重油燃焼火力発電所の煙灰から回収され
るバナジウム回収資源を利用することができるバナジウ
ム酸化物／チタニアハイブリッド光触媒とその製造方法
を提案するものである。In view of the above, the present invention has been made in view of the above-mentioned problems in titania and the characteristics required for the above-mentioned energy-minimum type environmental purification system. Thus, the present invention can decompose and remove pollutants with higher efficiency than titania, and is excellent in chemical stability and safety. The present invention proposes a vanadium oxide / titania hybrid photocatalyst which is easy to handle and can utilize vanadium recovery resources recovered from fumes of a heavy oil fired thermal power plant, and a method for producing the same.
【０００８】[0008]
【発明が解決するための手段】前記の目的を達成するた
め、本発明では、従来最も優れた光触媒とされるチタニ
アを取扱いが容易な形態としたマトリックスとして採用
し、これにバナジウム酸化物を固溶させた。In order to achieve the above object, the present invention employs titania, which is conventionally the most excellent photocatalyst, as a matrix in an easy-to-handle form, to which vanadium oxide is fixed. Was dissolved.
【０００９】すなわち、本発明によるバナジウム酸化物
／チタニアハイブリッド光触媒は、チタニアを主体とす
るが、このチタニアにバナジウム酸化物を含有させるこ
とにより、チタニア単体より高効率に環境汚染物質を分
解除去することを特徴とする。That is, the vanadium oxide / titania hybrid photocatalyst according to the present invention is mainly composed of titania. By adding vanadium oxide to this titania, it is possible to decompose and remove environmental pollutants more efficiently than titania alone. It is characterized by.
【００１０】バナジウム酸化物の含有率は、チタニアに
対して０．０１〜５ｗｔ％が最適である。基材となるチ
タニアは、繊維、多孔質体、多孔質薄膜、薄膜、鱗片
状、顆粒状のいずれかの形態のものか、或いは別の基材
の表面に多孔質体、多孔質薄膜、薄膜のいずれかの形態
でチタニアを形成することもできる。[0010] The content of vanadium oxide is optimally 0.01 to 5 wt% with respect to titania. The titania used as the base material may be in the form of fiber, porous body, porous thin film, thin film, flake, granule, or a porous body, porous thin film, thin film on the surface of another base material. The titania can be formed in any one of the above modes.
【００１１】このバナジウム酸化物／チタニアハイブリ
ッド光触媒では、バナジウム酸化物が実質的にチタニア
の表面近傍に偏在化している。このバナジウム酸化物
は、実質的にチタニアの表面近傍に固溶し、水に不溶で
ある。In this vanadium oxide / titania hybrid photocatalyst, the vanadium oxide is substantially localized near the surface of titania. This vanadium oxide is substantially dissolved in the vicinity of the surface of titania and is insoluble in water.
【００１２】前記のようなバナジウム酸化物／チタニア
ハイブリッド光触媒は、繊維、多孔質体、多孔質薄膜、
薄膜、鱗片状、粉末のいずれかであるチタニア、あるい
は、基材の表面に多孔質体、多孔質薄膜、薄膜のいずれ
かの形態のチタニアを形成する第一の工程と、このチタ
ニアにバナジウム化合物を含浸する第二の工程と、バナ
ジウム化合物を酸化分解してチタニアにバナジウム酸化
物を固溶させる第三の工程とを有する製造方法により製
造することができる。The above-described vanadium oxide / titania hybrid photocatalyst includes a fiber, a porous body, a porous thin film,
Thin film, scaly, powdery titania, or a porous body on the surface of the substrate, a porous thin film, the first step of forming titania in any form of a thin film, and a vanadium compound in the titania , And a third step of oxidatively decomposing the vanadium compound to form a solid solution of vanadium oxide in titania.
【００１３】例えば、繊維、多孔質体、多孔質薄膜、薄
膜、鱗片状、顆粒状のいずれかであるチタニアは、チタ
ンアルコキシドを原料として得られた前駆体を有機基材
に含浸した後、酸化分解して合成することにより得る。
また、基材の表面に形成された多孔質体、多孔質薄膜、
薄膜のいずれかの形態のチタニアは、多孔質体、多孔質
薄膜、薄膜のいずれかの形態のチタニアを、チタンアル
コキシドを原料として得られた前駆体を無機基材に含浸
した後、酸化分解して基材表面に合成することにより得
る。For example, titania in the form of a fiber, a porous material, a porous thin film, a thin film, a scale, or a granule is obtained by impregnating an organic substrate with a precursor obtained from a titanium alkoxide as a raw material, and then oxidizing the precursor. It is obtained by decomposition and synthesis.
Also, a porous body formed on the surface of the substrate, a porous thin film,
Titania in any form of thin film, porous body, porous thin film, titania in any form of thin film, after impregnating an inorganic substrate with a precursor obtained from titanium alkoxide as a raw material, oxidatively decompose To be synthesized on the surface of the base material.
【００１４】特に、チタニア繊維は、チタンアルコキシ
ドとβ−ジケトンを原料として得られた無機高分子を紡
糸した後、酸化分解して合成することができる。チタニ
アにバナジウム化合物を含浸する第二の工程は、例え
ば、五酸化バナジウムをエチレンジアミン、ジエチレン
トリアミンなどの有機塩基水溶液に溶解して含浸する。In particular, titania fibers can be synthesized by spinning an inorganic polymer obtained from titanium alkoxide and β-diketone as raw materials and then oxidatively decomposing the same. In the second step of impregnating titania with a vanadium compound, for example, vanadium pentoxide is dissolved and impregnated in an aqueous solution of an organic base such as ethylenediamine or diethylenetriamine.
【００１５】バナジウム化合物を酸化分解してチタニア
にバナジウム酸化物を固溶させる第三の工程において
は、４００〜８００℃の温度でバナジウム化合物を酸化
分解してチタニアにバナジウム酸化物を固溶させる。さ
らに、この第三の工程の後に、第四の工程として水洗
後、乾燥を行うことが好ましい。In the third step of oxidatively decomposing the vanadium compound to form a solid solution of vanadium oxide in titania, the vanadium compound is oxidatively decomposed at a temperature of 400 to 800 ° C. to form a solid solution of the vanadium oxide in titania. Further, after the third step, it is preferable to perform washing and drying as a fourth step.
【００１６】[0016]
【発明の実施の形態】次に、本発明の実施の形態につい
て、具体的且つ詳細に説明する。前述したように、本発
明による光触媒は、取扱いが容易な形態を有するチタニ
アにバナジウム酸化物を固溶させたものである。Next, embodiments of the present invention will be described specifically and in detail. As described above, the photocatalyst according to the present invention is obtained by dissolving vanadium oxide in titania having an easily handled form.
【００１７】このようなバナジウム酸化物／チタニアハ
イブリッド光触媒は、繊維、多孔質体、多孔質薄膜、薄
膜、鱗片状、顆粒状のいずれかであるチタニア、あるい
は、基材の表面に多孔質体、多孔質薄膜、薄膜のいずれ
かの形態のチタニアを形成する第一の工程と、このチタ
ニアにバナジウム化合物を含浸する第二の工程と、バナ
ジウム化合物を酸化分解してチタニアにバナジウム酸化
物を固溶させる第三の工程とを経ることにより製造する
ことができる。Such a vanadium oxide / titania hybrid photocatalyst is prepared from a fiber, a porous material, a porous thin film, a thin film, a flaky or granular titania, or a porous material on the surface of a substrate. A first step of forming titania in any form of a porous thin film or a thin film, a second step of impregnating the titania with a vanadium compound, and oxidizing and decomposing the vanadium compound to form a solid solution of vanadium oxide in titania And a third step.
【００１８】本発明の第一の工程で合成される繊維、多
孔質体、多孔質薄膜、薄膜、鱗片状、顆粒状のいずれか
の形態を有するチタニアは、チタンアルコキシドを原料
として得られた前駆体を有機基材に含浸した後、酸化分
解して合成することができる。チタンアルコキシドを原
料として得られる前駆体は、例えばチタンテトライソプ
ロポキシド、チタンテトラ−ｎ−ブトキシドなどのヘキ
サンやベンゼン溶液、あるいはゾル−ゲル法を利用して
合成される無機高分子を利用することができる。有機基
材は、繊維、多孔質体、多孔質薄膜、薄膜、鱗片状、顆
粒状のいずれかの形態を有する有機高分子を利用するこ
とができ、セルロース、ポリウレタン、フェノール樹
脂、ポリビニルアルコールなど酸化分解により残留物が
ないものが好適である。The titania synthesized in the first step of the present invention, which has any one of the form of fiber, porous body, porous thin film, thin film, scale, or granule, is a precursor obtained by using titanium alkoxide as a raw material. After the body is impregnated with an organic substrate, it can be synthesized by oxidative decomposition. The precursor obtained from titanium alkoxide as a raw material may be, for example, a hexane or benzene solution such as titanium tetraisopropoxide or titanium tetra-n-butoxide, or an inorganic polymer synthesized using a sol-gel method. Can be. As the organic base material, an organic polymer having any of a fiber, a porous body, a porous thin film, a thin film, a scale, and a granular form can be used, and oxidized cellulose, polyurethane, phenol resin, polyvinyl alcohol, and the like. Those which have no residue due to decomposition are preferred.
【００１９】また、チタニア繊維は一般的にゾル−ゲル
法を利用して合成されるが、チタンアルコキシドとβ−
ジケトンを原料として得られた無機高分子を紡糸した
後、酸化分解して合成する方法が好適である。該無機高
分子は本発明の第一の工程で他の形態のチタニアの合成
にも利用することができる。Titania fibers are generally synthesized using a sol-gel method, but titanium alkoxide and β-
A method of spinning an inorganic polymer obtained from a diketone as a raw material and then oxidatively decomposing the inorganic polymer to synthesize the polymer is preferable. The inorganic polymer can be used for the synthesis of other forms of titania in the first step of the present invention.
【００２０】基材の表面の多孔質体、多孔質薄膜、薄膜
のいずれかの形態を有するチタニアは、チタンアルコキ
シドを原料として得られた前駆体を無機基材に含浸した
後、酸化分解して合成することができる。その外に、熱
ＣＶＤ法や低温プラズマＣＶＤ法なども多孔質薄膜ある
いは薄膜の製造に利用できる。無機基材は、繊維、多孔
質体、鱗片状、顆粒状などの形態を有するセラミックス
を利用することができ、シリコンカーバイド、シリカ、
ジルコニア、アルミナなどが好適である。Titania having any of a porous body, a porous thin film, and a thin film on the surface of a base material is impregnated with an inorganic base material using a precursor obtained from a titanium alkoxide, and then oxidatively decomposed. Can be synthesized. In addition, a thermal CVD method, a low-temperature plasma CVD method, and the like can also be used for producing a porous thin film or a thin film. As the inorganic base material, fibers, porous bodies, flakes, ceramics having a form such as granules can be used, and silicon carbide, silica,
Zirconia, alumina and the like are preferred.
【００２１】前記第二の工程では、バナジウム化合物溶
液をチタニアに含浸する。バナジウム化合物としては、
五酸化バナジウムなどのバナジウム酸化物、メタバナジ
ン酸アンモニウム、オキシ塩化バナジウム、オキシ硫酸
バナジウム、トリイソプロポキシバナジル、トリ−ｎ−
ブトキシバナジルなどのアルコキシド、酸化バナジウム
アセチルアセトナートなどを使用することができる。こ
れらの化合物は、水溶液、或いは有機溶媒に溶解して使
用される。In the second step, the titania is impregnated with the vanadium compound solution. As the vanadium compound,
Vanadium oxides such as vanadium pentoxide, ammonium metavanadate, vanadium oxychloride, vanadium oxysulfate, triisopropoxyvanadyl, tri-n-
Alkoxides such as butoxyvanadyl, vanadium oxide acetylacetonate and the like can be used. These compounds are used after being dissolved in an aqueous solution or an organic solvent.
【００２２】五酸化バナジウムとメタバナジン酸アンモ
ニウムは、重油燃焼火力発電所の煙灰から回収されるバ
ナジウム回収資源である上に、これらを水、アンモニア
水、あるいは有機塩基水溶液に溶解してチタニアに含浸
した場合によい結果が得られることが見出された。特に
五酸化バナジウムをエチレンジアミン、ジエチレントリ
アミンなどの有機塩基水溶液に溶解して調製した溶液は
長時間にわたって安定で均一な含浸が可能である。Vanadium pentoxide and ammonium metavanadate are vanadium recovery resources recovered from the fumes of a heavy oil-fired thermal power plant. In addition, they were dissolved in water, aqueous ammonia, or an aqueous organic base solution and impregnated in titania. It has been found that good results are obtained in some cases. In particular, a solution prepared by dissolving vanadium pentoxide in an aqueous solution of an organic base such as ethylenediamine or diethylenetriamine can be stably and uniformly impregnated for a long time.
【００２３】トリイソプロポキシバナジル、トリ−ｎ−
ブトキシバナジルなどのアルコキシド、酸化バナジウム
アセチルアセトナートなどはアルコールなどの有機溶媒
に可溶であり、適度な加水分解によりゾルを形成するの
で、均一な含浸には好適であるが、高価であり長時間に
わたって安定なゾルを得ることは困難である。Triisopropoxyvanadyl, tri-n-
Alkoxides such as butoxyvanadyl, and vanadium oxide acetylacetonate are soluble in organic solvents such as alcohols and form sols by appropriate hydrolysis, so they are suitable for uniform impregnation, but are expensive and prolonged. It is difficult to obtain a stable sol over a wide range.
【００２４】上述のバナジウム化合物溶液の濃度は、１
〜５０％でよいが、特にこの範囲に限定されるものでは
ない。含浸後、余分なバナジウム化合物溶液はろ過など
により除去されるが、チタニアの形態により含浸量が決
まるので、バナジウム酸化物がチタニアに対して０．０
１〜５ｗｔ％含有されるようにバナジウム化合物溶液の
濃度を決めることができる。The concentration of the above-mentioned vanadium compound solution is 1
Although it may be up to 50%, it is not particularly limited to this range. After the impregnation, excess vanadium compound solution is removed by filtration or the like.However, since the amount of impregnation is determined by the form of titania, the vanadium oxide is 0.0
The concentration of the vanadium compound solution can be determined so as to contain 1 to 5 wt%.
【００２５】前記の第三の工程では、含浸したバナジウ
ム化合物を酸化分解してチタニアにバナジウム酸化物を
固溶させる。酸化分解は大気中あるいは酸素雰囲気中で
必要により水分を添加しながら、４００〜８００℃で焼
成することにより行うことができる。焼成温度が４００
℃より低い場合にはバナジウム酸化物の固溶が十分でな
かったり、炭素成分が残留して光触媒機能が低下する。
また、８００℃より高温での焼成ではチタニアの結晶相
がアナターゼからルチルに転換し始め、やはり光触媒機
能が低下するので好ましくない。In the third step, the impregnated vanadium compound is oxidatively decomposed to form a solid solution of vanadium oxide in titania. The oxidative decomposition can be carried out by baking at 400 to 800 ° C. in the air or an oxygen atmosphere while adding water as necessary. Firing temperature 400
When the temperature is lower than ℃, the vanadium oxide is not sufficiently dissolved, or the carbon component remains and the photocatalytic function deteriorates.
Further, firing at a temperature higher than 800 ° C. is not preferable because the crystalline phase of titania starts to be converted from anatase to rutile, and the photocatalytic function is also lowered.
【００２６】さらにこの第三の工程の後、必要により第
四の工程として水洗後、乾燥を行うことができる。本発
明のバナジウム酸化物／チタニアハイブリッド光触媒は
チタニアにバナジウム酸化物を固溶さるためバナジウム
酸化物が分離したり水中に溶出することはないが、含浸
量が多い場合にはチタニア表面にバナジウム酸化物が偏
析し、それが分離したり水中に溶出することがある。そ
こで、その様な場合には第三の工程の後、第四の工程と
して水洗を行なった後、乾燥して、チタニア表面に偏析
したバナジウム酸化物を除去することができる。After the third step, if necessary, a fourth step may be followed by washing with water and drying. Although the vanadium oxide / titania hybrid photocatalyst of the present invention dissolves vanadium oxide in titania, the vanadium oxide does not separate or elute into water. However, when the impregnation amount is large, the vanadium oxide is formed on the titania surface. May segregate and separate or elute in water. In such a case, after the third step, water washing is performed as a fourth step, followed by drying to remove vanadium oxide segregated on the titania surface.
【００２７】このようにして製造されたバナジウム酸化
物／チタニアハイブリッド光触媒はチタニアに対してバ
ナジウム酸化物が０．０１〜５ｗｔ％含有されている。
図１は、五酸化バナジウムと５ｗｔ％バナジウム酸化物
を含有したチタニア多孔質体のＸ線回折図形を示す。こ
の図１の双方のＸ線回折図形を比較しても明らかな通
り、バナジウム酸化物が５ｗｔ％含有されているチタニ
ア多孔質体のＸ線回折図形には五酸化バナジウムのピー
クは検出されず、固溶している。The vanadium oxide / titania hybrid photocatalyst thus produced contains 0.01 to 5% by weight of vanadium oxide with respect to titania.
FIG. 1 shows an X-ray diffraction pattern of a titania porous body containing vanadium pentoxide and 5 wt% vanadium oxide. As is clear from the comparison of the X-ray diffraction patterns of both FIGS. 1A and 1B, no peak of vanadium pentoxide was detected in the X-ray diffraction pattern of the titania porous body containing 5 wt% of vanadium oxide. Solid solution.
【００２８】チタニアに対するバナジウム酸化物の含有
量は、特に、環境汚染物質の分解効率に影響を与える。
チタニアに対してバナジウム酸化物が０．０１ｗｔ％よ
り小さいと効果が現れず、５ｗｔ％より多く含有させる
とチタニアより反応効率が低くなる。The content of vanadium oxide with respect to titania particularly affects the decomposition efficiency of environmental pollutants.
If the vanadium oxide is less than 0.01 wt% with respect to titania, no effect is exhibited, and if the content is more than 5 wt%, the reaction efficiency is lower than that of titania.
【００２９】前述のバナジウム酸化物／チタニアハイブ
リッド光触媒の製造方法において、第一の工程と第二の
工程を逆にしてバナジウム酸化物をチタニア内部にのみ
含有させた場合には、バナジウム酸化物を含有させた効
果はまったく見られなかったことから、実質的にチタニ
アの表面近傍に偏在化しているバナジウム酸化物が有効
であることがわかる。In the above-described method for producing a vanadium oxide / titania hybrid photocatalyst, when the vanadium oxide is contained only inside the titania by reversing the first step and the second step, the vanadium oxide is contained. Since no effect was observed at all, it can be seen that vanadium oxide which is substantially localized near the surface of titania is effective.
【００３０】バナジウム酸化物が０．０１〜５ｗｔ％含
有されている場合にチタニアより反応効率が高くなる理
由は必ずしも明らかではないが、バナジウム酸化物／チ
タニアハイブリッド光触媒がわずかに着色していること
から可視光が光反応に利用されること、比表面積の拡
大、有害物質の吸着サイトの増加、酸化−還元サイト分
離などの効果が相乗的に作用していると推定される。The reason why the reaction efficiency is higher than that of titania when the content of vanadium oxide is 0.01 to 5% by weight is not necessarily clear, but the reason is that the vanadium oxide / titania hybrid photocatalyst is slightly colored. It is presumed that effects such as the use of visible light for photoreaction, an increase in specific surface area, an increase in harmful substance adsorption sites, and separation of oxidation-reduction sites are synergistically acting.
【００３１】このようなバナジウム酸化物／チタニアハ
イブリッド光触媒は、実質的に光が照射される表面が１
００％の光触媒である。その形態は取扱いが容易な繊
維、多孔質体、多孔質薄膜、薄膜、鱗片状、顆粒状のい
ずれかであり、このままでモジュール化して環境浄化シ
ステムに組み込むことができるいわゆる自立型光触媒で
ある。Such a vanadium oxide / titania hybrid photocatalyst has a surface to be substantially irradiated with light.
00% photocatalyst. The form is any of fiber, porous body, porous thin film, thin film, scale, and granule that can be easily handled, and is a so-called self-supporting photocatalyst that can be modularized as it is and incorporated into an environmental purification system.
【００３２】[0032]
【実施例】次に、本発明の実施例として、バナジウム酸
化物／チタニアハイブリッド光触媒の具体的な製造方法
と、製造したバナジウム酸化物／チタニアハイブリッド
光触媒の特性について具体的に説明する。EXAMPLES Next, as an example of the present invention, a specific method for producing a vanadium oxide / titania hybrid photocatalyst and characteristics of the produced vanadium oxide / titania hybrid photocatalyst will be specifically described.
【００３３】（実施例１）チタンテトライソプロポキシ
ドにβ−ジケトンであるエチルアセトアセテートの当量
を加え、これをエタノールで希釈した後、塩酸とエタノ
ールの混合液を滴下しながら１時間攪拌した。その後、
ロータリーエバポレーターで濃縮を行い、チタニアの前
駆体である無機高分子を得た。Example 1 An equivalent amount of ethyl acetoacetate, a β-diketone, was added to titanium tetraisopropoxide, and the mixture was diluted with ethanol. The mixture was stirred for 1 hour while dropwise adding a mixture of hydrochloric acid and ethanol. afterwards,
Concentration was performed using a rotary evaporator to obtain an inorganic polymer that was a precursor of titania.
【００３４】このチタニアの前駆体である無機高分子を
紡糸した後、５０℃の水蒸気中で０．５時間処理し、大
気中で１時間に１００℃の昇温速度で５００℃まで加熱
し、５００℃で１時間保持して、直径約１０μｍのチタ
ニア繊維を得た。この結晶相はアナターゼであった。After spinning the inorganic polymer which is a precursor of titania, it is treated in steam at 50 ° C. for 0.5 hour, and heated to 500 ° C. in the atmosphere at a rate of 100 ° C./hour. It was kept at 500 ° C. for 1 hour to obtain titania fibers having a diameter of about 10 μm. This crystalline phase was anatase.
【００３５】このチタニア繊維を、五酸化バナジウムを
エチレンジアミン水溶液に溶解して、濃度をそれぞれ
０．００４、０．０４、０．２、２ｗｔ％に調製した溶
液に１時間含浸し、その後、ろ過して乾燥した。これら
の繊維を大気中で１時間に１００℃の昇温速度で５００
℃まで加熱し、５００℃で１時間保持して、バナジウム
酸化物／チタニアハイブリッド光触媒繊維を合成した。
これらの繊維はそれぞれ、０．０１、０．１、０．５、
５ ｗｔ％の重量増加を示したので、以後０．０１ｗｔ
％−Ｖ2Ｏ5／ＴｉＯ2繊維、０．１ｗｔ％−Ｖ2Ｏ5／Ｔ
ｉＯ2繊維、０．５ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2繊維、５ｗ
ｔ％−Ｖ2Ｏ5／ＴｉＯ2繊維と称する。The titania fiber was impregnated with a solution prepared by dissolving vanadium pentoxide in an aqueous solution of ethylenediamine and adjusting the concentration to 0.004, 0.04, 0.2, and 2% by weight for 1 hour, followed by filtration. And dried. These fibers are heated in air at a rate of 100 ° C./hour for 500 hours.
C., and kept at 500.degree. C. for 1 hour to synthesize a vanadium oxide / titania hybrid photocatalytic fiber.
These fibers are 0.01, 0.1, 0.5,
5 wt% increase in weight, and thereafter 0.01 wt%
% -V 2 O 5 / TiO 2 fibers, 0.1wt% -V 2 O 5 / T
iO 2 fibers, 0.5wt% -V 2 O 5 / TiO 2 fibers, 5w
It referred to t% -V 2 O 5 / TiO 2 fibers.
【００３６】これら０．０１ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2
繊維、０．１ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2繊維、０．５ｗ
ｔ％−Ｖ2Ｏ5／ＴｉＯ2繊維、５ｗｔ％−Ｖ2Ｏ5／Ｔｉ
Ｏ2繊維をそれぞれ走査型電子顕微鏡（ＳＥＭ）により
観察した。その結果、５ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2繊維
でわずかに繊維表面に微粒子の存在が認められる以外
は、いずれも繊維表面にバナジウム酸化物の偏析は認め
られない。These 0.01 wt% -V 2 O 5 / TiO 2
Fibers, 0.1wt% -V 2 O 5 / TiO 2 fibers, 0.5 w
t% -V 2 O 5 / TiO 2 fibers, 5wt% -V 2 O 5 / Ti
Each of the O 2 fibers was observed with a scanning electron microscope (SEM). As a result, except for the presence of fine particles is observed slightly fiber surface with 5wt% -V 2 O 5 / TiO 2 fibers, segregation of vanadium oxide to both the fiber surface is not observed.
【００３７】これらの繊維を一昼夜水中に浸しておいた
場合のバナジウムの溶出量をＩＣＰ発光分析により調べ
た結果を、実施例２の多孔質体の場合とともに表１に示
す。溶出後のバナジウム酸化物／チタニアハイブリッド
光触媒からは実質的なバナジウムの溶出は認められなか
った。The results of examining the amount of vanadium eluted by ICP emission analysis when these fibers were immersed in water all day and night are shown in Table 1 together with the porous body of Example 2. No substantial vanadium elution was observed from the vanadium oxide / titania hybrid photocatalyst after the elution.
【００３８】次に、これらの繊維およびチタニア繊維を
それぞれ２００ｍｇ、内径８ｍｍの石英ガラス管に長さ
４ｃｍになるように充填し自立型光触媒モジュールとし
た。これらのモジュールにブラックライトを用い、２．
０ｍＷ／ｃｍ2の紫外線ＵＶＡを照射しながら、流通式
の装置により大気組成の気相中で代表的な環境汚染物質
である１０００ｐｐｍのトリクロロエチレンの分解を行
った。そして、ガスクロマトグラフでその分解効率の測
定を行なった。その結果、図２に示すように、Ｖ2Ｏ5の
含有率が０．１と０．５ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2繊維
では、トリクロロエチレンの分解効率がチタニアに対し
て３倍程度高くなった。分解は、トリクロロエチレンが
ほぼ二酸化炭素、水、および塩酸に分解される完全酸化
型であった。これは、環境浄化システムを設計する場合
に光触媒モジュールの大きさが１／３程度にできること
を示している。Next, 200 mg of each of these fibers and titania fiber was filled into a quartz glass tube having an inner diameter of 8 mm so as to have a length of 4 cm to obtain a self-supporting photocatalyst module. 1. These modules use black light.
While irradiating ultraviolet rays UVA at 0 mW / cm 2 , 1000 ppm of trichloroethylene, which is a typical environmental pollutant, was decomposed in a gas phase having an atmospheric composition by a flow-type apparatus. The decomposition efficiency was measured by gas chromatography. As a result, as shown in FIG. 2, in the V 2 O 5 content of 0.1 and 0.5 wt% -V 2 O 5 / TiO 2 fiber, the decomposition efficiency of trichlorethylene is about three times higher than that of titania. became. The decomposition was of the fully oxidized type, where trichlorethylene was almost decomposed into carbon dioxide, water and hydrochloric acid. This indicates that the size of the photocatalyst module can be reduced to about 1/3 when designing an environmental purification system.
【００３９】さらにこの実験では、図２に示すように、
Ｖ2Ｏ5の含有率が０．１と０．５ｗｔ％−Ｖ2Ｏ5／Ｔｉ
Ｏ2繊維を中心として、Ｖ2Ｏ5の含有率が０．０１〜５
ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2繊維において特に良好な分解
効率が得られていることが分かる。Further, in this experiment, as shown in FIG.
V 2 O 5 content of 0.1 and 0.5 wt% −V 2 O 5 / Ti
The content of V 2 O 5 is 0.01 to 5 around the O 2 fiber.
It can be seen that particularly good decomposition efficiency can be obtained in wt% -V 2 O 5 / TiO 2 fibers.
【００４０】（実施例２）チタンテトラ−ｎ−ブトキシ
ドの５０％ヘキサン溶液を調製し、チタニアの前駆体と
した。この溶液をセルロース製のろ紙と同様の構造を有
する直径約２ｍｍの粒状基材に含浸し、大気中で乾燥し
た後、大気中で１時間に２００℃の昇温速度で５００℃
まで加熱し、５００℃で２時間保持して、直径約１．５
ｍｍの粒状のチタニア多孔質体を得た。結晶相はアナタ
ーゼであった。Example 2 A 50% hexane solution of titanium tetra-n-butoxide was prepared and used as a precursor of titania. This solution is impregnated into a granular base material having a structure similar to that of a cellulose filter paper and having a diameter of about 2 mm, dried in the air, and then heated to a temperature of 500 ° C. at a rate of 200 ° C./hour in the air.
And hold at 500 ° C. for 2 hours.
mm of granular titania porous material was obtained. The crystalline phase was anatase.
【００４１】このチタニア多孔質体を、五酸化バナジウ
ムをエチレンジアミン水溶液に溶解して、濃度をそれぞ
れ０．００１、０．０１、０．０５、０．５ｗｔ％に調
製した溶液に１時間含浸し、その後、ろ過して乾燥し
た。これらの多孔質体を大気中で１時間に２００℃の昇
温速度で６００℃まで加熱し、６００℃で１時間保持し
て、バナジウム酸化物／チタニアハイブリッド多孔質光
触媒を合成した。これらの多孔質体はそれぞれ、０．０
１、０．１、０．５、５ ｗｔ％の重量増加を示したの
で、以後０．０１ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2多孔質体、
０．１ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2多孔質体、０．５ｗｔ
％−Ｖ2Ｏ5／ＴｉＯ2多孔質体、５ｗｔ％−Ｖ2Ｏ5／Ｔ
ｉＯ2多孔質体と称する。This porous titania material was impregnated with a solution prepared by dissolving vanadium pentoxide in an aqueous solution of ethylenediamine to a concentration of 0.001, 0.01, 0.05, and 0.5% by weight for 1 hour. Then, it was filtered and dried. These porous bodies were heated to 600 ° C. in the air at a rate of 200 ° C. for one hour, and maintained at 600 ° C. for one hour to synthesize a vanadium oxide / titania hybrid porous photocatalyst. Each of these porous bodies is 0.0
Since the weight increase of 1, 0.1, 0.5, and 5 wt% was shown, the porous body of 0.01 wt% -V 2 O 5 / TiO 2 was thereafter used.
0.1wt% -V 2 O 5 / TiO 2 porous material, 0.5 wt
% -V 2 O 5 / TiO 2 porous material, 5wt% -V 2 O 5 / T
It is referred to as an iO 2 porous body.
【００４２】５ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2多孔質体を走
査型電子顕微鏡（ＳＥＭ）により観察した。この結果、
Ｖ2Ｏ5／ＴｉＯ2多孔質体は明らかに繊維状のチタニア
が絡み合った多孔質構造であることを示し、比表面積は
およそ１０ｍ2／ｇで、バナジウム酸化物の含有量の増
加とともに増加の傾向を示した。The 5 wt% -V 2 O 5 / TiO 2 porous body was observed with a scanning electron microscope (SEM). As a result,
The V 2 O 5 / TiO 2 porous body clearly shows a porous structure in which fibrous titania is entangled, and has a specific surface area of about 10 m 2 / g, which increases with an increase in the content of vanadium oxide. Showed a trend.
【００４３】これらの多孔質体を一昼夜水中に浸してお
いた場合のバナジウムの溶出量をＩＣＰ発光分析により
調べた結果を実施例１の表１に示す。溶出後のバナジウ
ム酸化物／チタニアハイブリッド光触媒からは実質的な
バナジウムの溶出は認められなかった。The results obtained by examining the amount of vanadium eluted by ICP emission analysis when these porous bodies were immersed in water for 24 hours are shown in Table 1 of Example 1. No substantial vanadium elution was observed from the vanadium oxide / titania hybrid photocatalyst after the elution.
【００４４】[0044]
【表１】 [Table 1]
【００４５】次に、これらの多孔質体およびチタニア多
孔質体をそれぞれ１ｇ、内径８ｍｍの石英ガラス管に長
さ１５ｃｍになるように充填し、自立型光触媒モジュー
ルとした。これらのモジュールにブラックライトを用い
て２．０ｍＷ／ｃｍ2の紫外線ＵＶＡを照射しながら、
大気組成の気相中で流通式の装置により、代表的な難分
解性物質である飽和炭化水素の１０２ｐｐｍのエタンの
分解を行なった。その結果、０．１ｗｔ％および０．５
ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2繊維では難分解性物質である
エタンの場合でも、分解効率がチタニアのみのものに対
して２倍程度高くなった。分解はほぼ完全酸化型であっ
た。これは、環境浄化システムを設計する場合に光触媒
モジュールの大きさが１／２程度にできることを示して
いる。Next, 1 g of each of the porous body and the titania porous body was filled into a quartz glass tube having an inner diameter of 8 mm so as to have a length of 15 cm to obtain a self-standing photocatalyst module. While irradiating these modules with ultraviolet light UVA of 2.0 mW / cm 2 using a black light,
In a gas phase having an atmospheric composition, 102 ppm of ethane of saturated hydrocarbon, which is a typical hardly decomposable substance, was decomposed by a flow-through apparatus. As a result, 0.1 wt% and 0.5
Even if the wt% -V 2 O 5 / The TiO 2 fibers ethane is hardly decomposable substance decomposition efficiency was about two times higher to that of only titania. The decomposition was almost completely oxidized. This indicates that the size of the photocatalyst module can be reduced to about 1/2 when designing an environmental purification system.
【００４６】（実施例３）チタンテトラ−ｎ−ブトキシ
ドの５０％ヘキサン溶液を調製し、チタニアの前駆体と
した。この溶液を直径約１０ｍｍの多孔質シリカビーズ
基材に含浸し、大気中で乾燥した後、大気中で１時間に
２００℃の昇温速度で６００℃まで加熱し、６００℃で
１時間保持して、約４ｗｔ％のチタニア薄膜が表面に形
成された多孔質シリカビーズを得た。結晶相はアナター
ゼであった。Example 3 A 50% hexane solution of titanium tetra-n-butoxide was prepared and used as a precursor of titania. This solution is impregnated into a porous silica bead base material having a diameter of about 10 mm, dried in the air, heated to 600 ° C. in the air at a rate of 200 ° C. for 1 hour, and kept at 600 ° C. for 1 hour. Thus, porous silica beads having about 4 wt% of a titania thin film formed on the surface were obtained. The crystalline phase was anatase.
【００４７】このチタニア薄膜が表面に形成された多孔
質シリカビーズを、五酸化バナジウムの０．２％アンモ
ニア水溶液に１時間含浸し、その後、ろ過して乾燥し
た。これらの多孔質シリカビーズを、大気中で１時間に
２００℃の昇温速度で６００℃まで加熱し、６００℃で
１時間保持して、バナジウム酸化物／チタニアハイブリ
ッド光触媒が表面に形成された多孔質シリカビーズを合
成した。表面に形成されたバナジウム酸化物／チタニア
ハイブリッド光触媒は、０．５ｗｔ％のバナジウム酸化
物を含有する薄膜であった。The porous silica beads having the titania thin film formed on the surface were impregnated with a 0.2% aqueous solution of vanadium pentoxide for 1 hour, followed by filtration and drying. These porous silica beads are heated to 600 ° C. in the air at a rate of 200 ° C. for 1 hour and held at 600 ° C. for 1 hour to form a porous layer having a vanadium oxide / titania hybrid photocatalyst formed on the surface. Silica beads were synthesized. The vanadium oxide / titania hybrid photocatalyst formed on the surface was a thin film containing 0.5 wt% of vanadium oxide.
【００４８】次に、このバナジウム酸化物／チタニアハ
イブリッド光触媒が表面に形成された多孔質シリカビー
ズとチタニアが表面に形成された多孔質シリカビーズを
それぞれ１ ｇ、内径８ｍｍの石英ガラス管に長さ８
ｃｍになるように充填し自立型光触媒モジュールとし
た。これらのモジュールにブラックライトを用いて２．
０ｍＷ／ｃｍ2の紫外線ＵＶＡを照射しながら、大気組
成の気相中で流通式の装置により１０４ｐｐｍのトリク
ロロエチレンの分解を行なった。その結果、バナジウム
酸化物／チタニアハイブリッド光触媒が表面に形成され
た多孔質シリカビーズではトリクロロエチレンの分解効
率がチタニアが表面に形成された多孔質シリカビーズに
対して５倍程度高くなった。Next, 1 g of the porous silica beads having the vanadium oxide / titania hybrid photocatalyst formed on the surface thereof and 1 g of the porous silica beads having the titania formed on the surface thereof were placed in a quartz glass tube having an inner diameter of 8 mm. 8
cm to form a self-supporting photocatalyst module. 1. Using black light for these modules
While irradiating ultraviolet rays UVA of 0 mW / cm 2 , 104 ppm of trichlorethylene was decomposed by a flow-through apparatus in a gas phase having an atmospheric composition. As a result, the decomposition efficiency of trichlorethylene in the porous silica beads having the vanadium oxide / titania hybrid photocatalyst formed on the surface thereof was about five times higher than that of the porous silica beads having titania formed on the surface.
【００４９】（実施例４）実施例２で合成した０．０１
ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2多孔質体、０．１ｗｔ％−Ｖ2
Ｏ5／ＴｉＯ2多孔質体、０．５ｗｔ％−Ｖ2Ｏ5／ＴｉＯ
2多孔質体、５ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2多孔質体のそれ
ぞれ５００ｍｇを、濃度３０ｐｐｍのフェノール水溶液
３０ｍＬに添加し、太陽光シミュレーターにより５．８
ｍＷ／ｃｍ2で光照射を行なった。水溶液中のフェノー
ルの濃度および全有機炭素量を紫外−可視分光高度計お
よび全有機炭素測定装置で測定した結果、すべてのバナ
ジウム酸化物／チタニアハイブリッド光触媒でフェノー
ルの酸化生成物への転換速度がチタニア多孔質体の場合
より大きくなり、特に０．５ｗｔ％−Ｖ2Ｏ5／ＴｉＯ2
多孔質体で約１．５倍と最も大きくなった。Example 4 0.01 synthesized in Example 2
wt% -V 2 O 5 / TiO 2 porous material, 0.1 wt% -V 2
O 5 / TiO 2 porous body, 0.5 wt% -V 2 O 5 / TiO
2 porous body, each 500mg of 5wt% -V 2 O 5 / TiO 2 porous body was added to the aqueous phenol solution 30mL of concentration 30 ppm, 5.8 by solar simulator
Light irradiation was performed at mW / cm 2 . The concentration of phenol in the aqueous solution and the total amount of organic carbon were measured with an ultraviolet-visible spectrophotometer and a total organic carbon measuring device. As a result, the conversion rate of phenol to oxidation products in all vanadium oxide / titania hybrid photocatalysts was titania porous. becomes larger than the case of quality material, in particular 0.5wt% -V 2 O 5 / TiO 2
The maximum value was about 1.5 times for the porous body.
【００５０】[0050]
【発明の効果】以上説明した通り、本発明によれば、チ
タニアにバナジウム酸化物を固溶させることにより、チ
タニアより高効率での環境汚染物質の分解を可能とした
バナジウム酸化物／チタニアハイブリッド光触媒を得る
ことができる。しかも、重油燃焼火力発電所の煙灰から
回収される安価なバナジウム回収資源を利用することが
でき、その上、実質的に光が照射される表面が１００％
光触媒であり、その形態は、取扱いが容易な繊維、多孔
質体、多孔質薄膜、薄膜、鱗片状、顆粒状であるため、
このままでモジュール化して環境浄化システムに組み込
むことができるいわゆる自立型光触媒である。すなわ
ち、エネルギーミニマム型環境浄化システム用の光触媒
モジュールなどの開発の目的に合致した光触媒を得るこ
とができる。As described above, according to the present invention, a vanadium oxide / titania hybrid photocatalyst capable of decomposing environmental pollutants with higher efficiency than titania by making vanadium oxide form a solid solution in titania. Can be obtained. In addition, inexpensive vanadium recovery resources recovered from fumes from heavy oil-fired thermal power plants can be used, and the surface irradiated with light is substantially 100%.
It is a photocatalyst, its form is easy to handle fiber, porous body, porous thin film, thin film, scale-like, granular,
It is a so-called self-supporting photocatalyst that can be modularized as it is and incorporated into an environmental purification system. That is, it is possible to obtain a photocatalyst that meets the purpose of developing a photocatalyst module for an energy minimum type environmental purification system and the like.
【図面の簡単な説明】[Brief description of the drawings]
【図１】五酸化バナジウムと５ｗｔ％バナジウム酸化物
を含有したチタニア多孔質体のＸ線回折図形である。FIG. 1 is an X-ray diffraction pattern of a titania porous body containing vanadium pentoxide and 5 wt% vanadium oxide.
【図２】Ｖ2Ｏ5／ＴｉＯ2繊維のＶ2Ｏ5含有率とトリク
ロロエチレンの分解効率との関係を示すグラフである。FIG. 2 is a graph showing the relationship between the V 2 O 5 content of V 2 O 5 / TiO 2 fibers and the decomposition efficiency of trichlorethylene.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 35/04 Ｂ０１Ｊ 35/04 Ｂ Ｃ Ｚ 37/00 Ｇ 37/00 37/02 １０１Ｅ 37/02 １０１ １０１Ｄ ３０１Ｍ ３０１ Ｂ０１Ｄ 53/36 Ｃ Ｊ (72)発明者 蓼沼 克嘉 茨城県水戸市堀町字新田1044番地 株式会 社化研内 (72)発明者 古坂 寿啓 茨城県鹿嶋市宮中3833の18 Ｆターム(参考） 4D048 AA21 AB01 AB03 BA07X BA13X BA23X BB01 BB08 EA01 4G069 AA01 AA02 AA04 AA08 AA09 AA11 BA04A BA04B BA04C BA48A BA48C BB04A BB04B BB04C BB06A BB06B BB06C BC54A BC54B BC54C CA01 CA07 CA10 CA11 DA05 DA06 EA02X EA03X EA03Y EA04X EA04Y EA08 EB01 FA01 FA02 FA03 FA06 FB14 FB15 FB19 FB20 FB34 FB66 FB67──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 35/04 B01J 35/04 BC Z 37/00 G 37/00 37/02 101E 37/02 101 101D 301M 301 B01D 53/36 CJ (72) Inventor Katsuyoshi Tadenuma 1044 Nitta, Horicho, Mito-shi, Ibaraki Pref. Term (Reference) 4D048 AA21 AB01 AB03 BA07X BA13X BA23X BB01 BB08 EA01 4G069 AA01 AA02 AA04 AA08 AA09 AA11 BA04A BA04B BA04C BA48A BA48C BB04A BB04B BB04C BB06A BB06 CA04 EA0604 FA03 FA06 FB14 FB15 FB19 FB20 FB34 FB66 FB67
Claims (13)
ナジウム酸化物を含有させ、チタニアより高効率に環境
汚染物質を分解除去することを特徴とするバナジウム酸
化物／チタニアハイブリッド光触媒。1. A hybrid vanadium oxide / titania photocatalyst comprising titania as a main component, wherein the titania contains vanadium oxide to decompose and remove environmental pollutants with higher efficiency than titania.
０．０１〜５ｗｔ％含有することを特徴とする請求項１
に記載のバナジウム酸化物／チタニアハイブリッド光触
媒。2. The method according to claim 1, wherein the vanadium oxide is contained in an amount of 0.01 to 5% by weight based on titania.
2. The vanadium oxide / titania hybrid photocatalyst according to 1.
膜、薄膜、鱗片状、顆粒状のいずれかであることを特徴
とする請求項１または２に記載のバナジウム酸化物／チ
タニアハイブリッド光触媒。3. The hybrid vanadium oxide / titania photocatalyst according to claim 1, wherein the titania is one of a fiber, a porous body, a porous thin film, a thin film, a scale, and a granule.
質体、多孔質薄膜、薄膜のいずれかであることを特徴と
する請求項１または２に記載のバナジウム酸化物／チタ
ニアハイブリッド光触媒。4. The vanadium oxide / titania hybrid photocatalyst according to claim 1, wherein the titania is any one of a porous body, a porous thin film, and a thin film formed on the surface of the substrate.
表面近傍に偏在化していることを特徴とする請求項１〜
４の何れかに記載のバナジウム酸化物／チタニアハイブ
リッド光触媒。5. The method according to claim 1, wherein the vanadium oxide is substantially localized near the surface of the titania.
5. The vanadium oxide / titania hybrid photocatalyst according to any one of 4.
表面近傍に固溶し、水に不溶であることを特徴とする請
求項１〜５の何れかに記載のバナジウム酸化物／チタニ
アハイブリッド光触媒。6. The hybrid vanadium oxide / titania photocatalyst according to claim 1, wherein the vanadium oxide is substantially dissolved in the vicinity of the surface of titania and is insoluble in water.
ド光触媒を製造する方法であって、繊維、多孔質体、多
孔質薄膜、薄膜、鱗片状、粉末のいずれかであるチタニ
ア、あるいは、基材の表面に多孔質体、多孔質薄膜、薄
膜のいずれかの形態のチタニアを形成する第一の工程
と、このチタニアにバナジウム化合物を含浸する第二の
工程と、バナジウム化合物を酸化分解してチタニアにバ
ナジウム酸化物を固溶させる第三の工程とを有すること
を特徴とするバナジウム酸化物／チタニアハイブリッド
光触媒の製造方法。7. A method for producing a vanadium oxide / titania hybrid photocatalyst, comprising titania which is one of a fiber, a porous body, a porous thin film, a thin film, a flake, and a powder, or a surface of a substrate. A first step of forming titania in any form of a porous body, a porous thin film, and a thin film; a second step of impregnating the titania with a vanadium compound; and oxidizing and decomposing the vanadium compound to form vanadium oxide into titania. And a third step of solid-solving the substance. A method for producing a vanadium oxide / titania hybrid photocatalyst, comprising:
片状、顆粒状のいずれかであるチタニアを、チタンアル
コキシドを原料として得られた前駆体を有機基材に含浸
した後、酸化分解して合成することを特徴とする請求項
７に記載のバナジウム酸化物／チタニアハイブリッド光
触媒の製造方法。8. An organic substrate is impregnated with a precursor obtained from a titanium alkoxide as raw material by titania, which is one of a fiber, a porous body, a porous thin film, a thin film, a scale and a granule, and then oxidized. The method for producing a vanadium oxide / titania hybrid photocatalyst according to claim 7, wherein the photocatalyst is synthesized by decomposition.
の形態のチタニアを、チタンアルコキシドを原料として
得られた前駆体を無機基材に含浸した後、酸化分解して
基材表面に合成することを特徴とする請求項７に記載の
バナジウム酸化物／チタニアハイブリッド光触媒の製造
方法。9. Titanium in any form of a porous body, a porous thin film, and a thin film is impregnated with a precursor obtained from a titanium alkoxide as a raw material, and then oxidatively decomposed to a surface of the base material. The method for producing a vanadium oxide / titania hybrid photocatalyst according to claim 7, which is synthesized.
β−ジケトンを原料として得られた無機高分子を紡糸し
た後、酸化分解して合成することを特徴とする請求項７
に記載のバナジウム酸化物／チタニアハイブリッド光触
媒の製造方法。10. The titania fiber is synthesized by spinning an inorganic polymer obtained using titanium alkoxide and β-diketone as raw materials and then oxidatively decomposing the same.
3. The method for producing a vanadium oxide / titania hybrid photocatalyst according to 1.
溶解して含浸することを特徴とする請求項７に記載のバ
ナジウム酸化物／チタニアハイブリッド光触媒の製造方
法。11. The method for producing a vanadium oxide / titania hybrid photocatalyst according to claim 7, wherein vanadium pentoxide is dissolved and impregnated in an aqueous organic base solution.
ニアにバナジウム酸化物を固溶させる温度が４００〜８
００℃であることを特徴とする請求項７〜１１の何れか
に記載のバナジウム酸化物／チタニアハイブリッド光触
媒の製造方法。12. A temperature at which a vanadium oxide is solid-dissolved in titania by oxidative decomposition of a vanadium compound is 400 to 8;
The method for producing a vanadium oxide / titania hybrid photocatalyst according to any one of claims 7 to 11, wherein the temperature is 00 ° C.
ニアにバナジウム酸化物を固溶させる第三の工程の後
に、第四の工程として水洗後、乾燥を行うことを特徴と
する請求項７〜１２の何れかに記載のバナジウム酸化物
／チタニアハイブリッド光触媒の製造方法。13. The method according to claim 7, wherein after the third step of oxidatively decomposing the vanadium compound to form a solid solution of the vanadium oxide in titania, washing and drying are performed as a fourth step. The method for producing a vanadium oxide / titania hybrid photocatalyst according to any one of the above.
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| JP2001096154A true JP2001096154A (en) | 2001-04-10 |
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| KR100395264B1 (en) * | 2001-05-15 | 2003-08-21 | 주식회사 엔바이오니아 | Photocatalytic composition having functions of air purification and antimicrobial activity and a moth-proof net coated with the composition |
| KR100565940B1 (en) | 2004-12-02 | 2006-03-30 | 한국과학기술연구원 | Vanadia-titania aerogel catalysts, preparing method of the same, and oxidative destruction of chlorinated aromatic compounds using the same |
| JP2008222654A (en) * | 2007-03-14 | 2008-09-25 | Nissan Chem Ind Ltd | Vitamin b12-titania hybrid compound and dehalogenation catalyst |
| KR101276240B1 (en) * | 2011-10-10 | 2013-06-20 | 인하대학교 산학협력단 | Preparation method of vanadium pentoxide coated titanium oxide powder using thermal plasma, and the vanadium pentoxide coated titanium oxide powder thereby |
| JP2015521104A (en) * | 2012-05-25 | 2015-07-27 | エルジー・ハウシス・リミテッドＬｇ Ｈａｕｓｙｓ，Ｌｔｄ． | Photocatalyst material, method for producing the same, and photocatalyst apparatus |
| KR20190054821A (en) * | 2017-11-14 | 2019-05-22 | 한국생산기술연구원 | Photocatalytic filter and manufacturing method thereof |
| CN113171769A (en) * | 2021-05-12 | 2021-07-27 | 周口师范学院 | Nano composite photocatalytic material and preparation method thereof |
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| KR20190054821A (en) * | 2017-11-14 | 2019-05-22 | 한국생산기술연구원 | Photocatalytic filter and manufacturing method thereof |
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| CN113171769A (en) * | 2021-05-12 | 2021-07-27 | 周口师范学院 | Nano composite photocatalytic material and preparation method thereof |
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