JPH11333301A - Photocatalyst having visible light activity and its use - Google Patents
Photocatalyst having visible light activity and its useInfo
- Publication number
- JPH11333301A JPH11333301A JP10141983A JP14198398A JPH11333301A JP H11333301 A JPH11333301 A JP H11333301A JP 10141983 A JP10141983 A JP 10141983A JP 14198398 A JP14198398 A JP 14198398A JP H11333301 A JPH11333301 A JP H11333301A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- catalyst
- light
- water
- air
- 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.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 66
- 230000000694 effects Effects 0.000 title claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 241000894006 Bacteria Species 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 230000035945 sensitivity Effects 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 230000001699 photocatalysis Effects 0.000 claims description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 230000001877 deodorizing effect Effects 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004887 air purification Methods 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 claims 2
- 238000000746 purification Methods 0.000 claims 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005211 surface analysis Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 titanium alkoxide Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、可視光活性を有す
る光触媒及びこの触媒を用いた可視光線を含む光を用い
る光分解方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst having visible light activity and a photodecomposition method using the catalyst and using light containing visible light.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】光触媒
を用いて脱臭や殺菌を行うことは種々検討され、実用化
されているものもある。例えば、ＷＯ９４／１１０９２
号には室内照明下における光触媒による空気処理方法が
開示されている。また特開平７−１０２６７８号には、
光触媒を用いた院内感染の防止方法が開示れている。い
ずれの場合も、酸化チタン等の酸化物半導体を光触媒と
して用いるものであり、励起光として４００ｎｍ以下の
紫外線が必要である。2. Description of the Related Art Deodorization and sterilization using a photocatalyst have been studied variously, and some of them have been put to practical use. For example, WO94 / 11092
Discloses an air treatment method using a photocatalyst under room lighting. Also, JP-A-7-102678 discloses that
A method for preventing hospital-acquired infection using a photocatalyst is disclosed. In each case, an oxide semiconductor such as titanium oxide is used as a photocatalyst, and ultraviolet light of 400 nm or less is required as excitation light.
【０００３】ところが、励起光源となる太陽光や人工光
には、紫外線以外に可視光線も含まれている。しかし、
上記酸化チタン等の酸化物半導体からなる光触媒では、
可視光線は利用されておらず、エネルギー変換効率とい
う観点からは、非常に非効率的であった。酸化チタンに
金属イオンをイオン注入法により注入することにより可
視光領域でも光触媒活性が得られることは知られている
が、方法が大がかりであり、実用化にはほど遠い。However, sunlight or artificial light serving as an excitation light source includes visible light in addition to ultraviolet light. But,
In the photocatalyst comprising an oxide semiconductor such as the above-described titanium oxide,
No visible light was used and it was very inefficient from the viewpoint of energy conversion efficiency. It is known that the photocatalytic activity can be obtained even in the visible light region by injecting metal ions into titanium oxide by an ion implantation method, but the method is extensive and is far from practical use.
【０００４】ところで、酸化チタンにプラズマCVD法に
よりTiCコーティングをすることで、紫外線による触媒
活性を向上させることができることが報告されている
(特開平9-87857号公報)。しかし、TiCコーティングによ
って可視光線による光触媒活性が得られるとは記載され
ていない。By the way, it has been reported that the catalytic activity by ultraviolet rays can be improved by coating TiC with titanium oxide by a plasma CVD method.
(JP-A-9-87857). However, it is not described that a photocatalytic activity by visible light can be obtained by the TiC coating.
【０００５】そこで本発明の第１の目的は、可視光線も
利用可能な新たな光触媒を提供することにある。Accordingly, a first object of the present invention is to provide a new photocatalyst that can also use visible light.
【０００６】さらに本発明の第２の目的は、上記新たな
光触媒を利用して有機物や細菌を含む種々の物質を光分
解して除去する方法を提供することにある。さらに本発
明の第３の目的は、上記新たな光触媒を用いた装置を提
供することにある。A second object of the present invention is to provide a method for photodecomposing and removing various substances including organic substances and bacteria using the above-mentioned new photocatalyst. Further, a third object of the present invention is to provide an apparatus using the new photocatalyst.
【０００７】[0007]
【課題を解決するための手段】本発明は、酸化チタンを
主成分とする光触媒であって、Ｘ線光電子分光法により
特定される酸素の１ｓ電子（但し、感度係数は０．７３
３）に帰属されるピークとチタンの２ｐ電子（但し、感
度係数は２．０７７）に帰属されるピークの面積比（Ｏ
１ｓ／Ｔｉ２ｐ）が２．４０以下であることを特徴とす
る触媒に関する。The present invention relates to a photocatalyst containing titanium oxide as a main component, wherein the photocatalyst is a 1 s electron of oxygen specified by X-ray photoelectron spectroscopy (the sensitivity coefficient is 0.73
3) and the area ratio (O) of the peak attributed to titanium 2p electrons (the sensitivity coefficient being 2.077).
(1s / Ti2p) is 2.40 or less.
【０００８】さらに本発明は、少なくとも可視光線を含
む光を照射した上記本発明の触媒に被分解物を接触させ
ることを特徴とする物質の分解方法、少なくとも可視光
線を含む光を照射した上記本発明の触媒に被分解物を含
む空気を接触させることを特徴とする空気の浄化方法、
及び少なくとも可視光線を含む光を照射した上記本発明
の触媒に被分解物を含む水を接触させることを特徴とす
る水の浄化方法に関する。Further, the present invention provides a method for decomposing a substance, which comprises contacting an object to be decomposed with the catalyst of the present invention irradiated with at least light containing visible light. An air purification method, comprising contacting air containing a decomposed substance with the catalyst of the present invention,
And a method for purifying water, comprising contacting water containing decomposed substances with the catalyst of the present invention irradiated with light containing at least visible light.
【０００９】また、本発明は、上記本発明の触媒を担体
に担持したことを特徴とする物品に関する。さらに本発
明は上記本発明の触媒または物品を含む装置であって、
前記装置が水清浄装置、空気清浄装置、殺菌装置、脱臭
装置、照明装置、光電池、及び水の分解装置からなる群
から選ばれることを特徴とする装置に関する。The present invention also relates to an article characterized in that the above-mentioned catalyst of the present invention is supported on a carrier. Further, the present invention is an apparatus comprising the above-described catalyst or article of the present invention,
The present invention relates to a device, wherein the device is selected from the group consisting of a water purifying device, an air purifying device, a sterilizing device, a deodorizing device, a lighting device, a photovoltaic cell, and a water decomposing device.
【００１０】[0010]
【発明の実施の形態】以下本発明についてさらに説明す
る。本発明の光触媒は、酸化チタンを主成分とする光触
媒である。酸化チタンは、光活性という観点からは、ア
ナターゼ型であることが好ましいが、一部がルチル型で
あってもよい。さらに本発明の光触媒は、Ｘ線光電子分
光法により特定される酸素の１ｓ電子（但し、感度係数
は０．７３３）に帰属されるピークとチタンの２ｐ電子
（但し、感度係数は２．０７７）に帰属されるピークの
面積比（Ｏ１ｓ／Ｔｉ２ｐ）が２．４０以下であること
を特徴とする。通常の酸化チタンのピーク面積比（Ｏ１
ｓ／Ｔｉ２ｐ）は、約２．５０である。それに対して本
発明の光触媒は、上記ピーク面積比（Ｏ１ｓ／Ｔｉ２
ｐ）が、２．４０以下、好ましくは２．３９以下であ
る。Ｘ線光電子分光法により特定されるピーク面積比
（Ｏ１ｓ／Ｔｉ２ｐ）は、酸化チタン表面の酸素欠陥き
程度を示す指標である。可視光に対して強い光活性を有
するためには、上記Ｘ線光電子分光法により特定される
ピーク面積比（Ｏ１ｓ／Ｔｉ２ｐ）が、２．４０以下、
好ましくは２．３９以下であることが必要である。ピー
ク面積比（Ｏ１ｓ／Ｔｉ２ｐ）が、２．４０を超えると
可視光活性は急激に低下する。また、ピーク面積比（Ｏ
１ｓ／Ｔｉ２ｐ）の下限は明らかでないが、例えば、
２．００程度である。あまりに酸素欠陥が多くなると、
結晶の安定性を阻害し、酸化チタンの光活性を低下させ
る可能性がある。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below. The photocatalyst of the present invention is a photocatalyst containing titanium oxide as a main component. Titanium oxide is preferably an anatase type from the viewpoint of photoactivity, but may be partially rutile. Further, the photocatalyst of the present invention has a peak attributed to the 1s electron of oxygen specified by X-ray photoelectron spectroscopy (provided that the sensitivity coefficient is 0.733) and a 2p electron of titanium (provided that the sensitivity coefficient is 2.077). Is characterized in that the peak area ratio (O1s / Ti2p) attributed to is 2.40 or less. Normal titanium oxide peak area ratio (O1
s / Ti2p) is about 2.50. On the other hand, the photocatalyst of the present invention has the peak area ratio (O1s / Ti2
p) is 2.40 or less, preferably 2.39 or less. The peak area ratio (O1s / Ti2p) specified by X-ray photoelectron spectroscopy is an index indicating the degree of oxygen vacancy on the titanium oxide surface. In order to have strong photoactivity with respect to visible light, the peak area ratio (O1s / Ti2p) specified by the X-ray photoelectron spectroscopy is 2.40 or less.
Preferably, it is necessary to be 2.39 or less. When the peak area ratio (O1s / Ti2p) exceeds 2.40, the visible light activity sharply decreases. In addition, the peak area ratio (O
Although the lower limit of 1s / Ti2p) is not clear, for example,
It is about 2.00. If there are too many oxygen defects,
It may inhibit the stability of the crystal and reduce the photoactivity of titanium oxide.
【００１１】上記範囲のピーク面積比（Ｏ１ｓ／Ｔｉ２
ｐ）を有することで、可視光活性及び紫外光活性を有す
る光触媒が得られる。特に、４００ｎｍ以上の光をカッ
トしたブラックライト光照射下における光触媒活性を１
００とした場合、４２０ｎｍ以下の光をカットしたハロ
ゲンランプ光照射下における光触媒活性が少なくとも１
０、好ましくは２０以上である高い可視光活性を有する
光触媒が得られる。尚、ここで光触媒活性とは、単位重
量の光触媒によるアセトアルデヒドの気相における分解
速度である。The peak area ratio in the above range (O1s / Ti2
By having p), a photocatalyst having visible light activity and ultraviolet light activity can be obtained. In particular, the photocatalytic activity under irradiation of black light, which cuts light of 400 nm or more, is 1
When the value is set to 00, the photocatalytic activity under irradiation of halogen lamp light which cuts light of 420 nm or less is at least 1
A photocatalyst having a high visible light activity of 0, preferably 20 or more is obtained. Here, the photocatalytic activity is the rate of decomposition of acetaldehyde in the gas phase by a unit weight of photocatalyst.
【００１２】また、本発明の光触媒は、酸化チタン表面
の一部に炭素系析出物を有することが好ましい。但し、
炭素系析出物が酸化チタン表面の全面を覆ってしまう
と、光触媒が得にくくなる場合がある。上記炭素系析出
物は、例えば、グラファイト、アモルファスカーボン、
ダイヤモンドライクカーボン、ダイヤモンド及び炭化水
素の少なくとも1種であり、通常、少なくともダイヤモ
ンドライクカーボン及び炭化水素(CH)を含むものである
ことができる。The photocatalyst of the present invention preferably has a carbon-based precipitate on a part of the surface of titanium oxide. However,
If the carbon-based precipitate covers the entire surface of the titanium oxide, it may be difficult to obtain a photocatalyst. The carbon-based precipitate is, for example, graphite, amorphous carbon,
It is at least one kind of diamond-like carbon, diamond, and hydrocarbon, and can usually contain at least diamond-like carbon and hydrocarbon (CH).
【００１３】さらに本発明の上記光触媒は、実質的に炭
化チタンの担持物を有さない。特開平9-87857号公報に
記載の酸化チタンは、炭化チタンのコーティングを有す
る光触媒であるが、本発明の光触媒はこれとは異なる。
さらに本発明の光触媒は、ＴＯＦ−ＳＩＭＳで測定した
Ｎａイオン量が全陽イオン量の１０％以上であることが
好ましい。より好ましくは、ＴＯＦ−ＳＩＭＳで測定し
たＮａイオン量が全陽イオン量の２０％以上である。ピ
ーク面積比（Ｏ１ｓ／Ｔｉ２ｐ）が小さくなり、酸素欠
陥が多くなるとＮａイオン量は増加する傾向がある。Further, the photocatalyst of the present invention has substantially no support of titanium carbide. The titanium oxide described in JP-A-9-87857 is a photocatalyst having a coating of titanium carbide, but the photocatalyst of the present invention is different from this.
Furthermore, in the photocatalyst of the present invention, the amount of Na ions measured by TOF-SIMS is preferably 10% or more of the total amount of cations. More preferably, the amount of Na ions measured by TOF-SIMS is 20% or more of the total amount of cations. When the peak area ratio (O1s / Ti2p) decreases and the number of oxygen vacancies increases, the amount of Na ions tends to increase.
【００１４】このような本発明の光触媒は、例えば、以
下の方法により製造することができる。本発明の光触媒
は、炭素源となる物質、水素源となる物質に電磁波を照
射してCHラジカル及びHラジカルを発生させ、これらの
ラジカルに酸化チタンを暴露する方法であって、上記ラ
ジカルの発生を不活性ガスの存在下で行うことで製造す
ることができる。CHラジカル及びHラジカルの発生を不
活性ガスの存在下で行うことで、電磁波の出力によって
は、例えば、４００Ｗのマイクロ波では、CHラジカルの
385nmにおける発光ピークの強度がHラジカルの655nmに
おける発光ピークの強度より強い、プラズマを得ること
ができる。不活性ガスの存在量は、CHラジカルの385nm
における発光ピークの強度とHラジカルの655nmにおける
発光ピークの強度とを考慮して適宜決定できる。ラジカ
ルへの暴露工程は、CHラジカルの385nmにおける発光ピ
ークの強度がHラジカルの655nmにおける発光ピークの強
度より強い条件下で行うことが好ましいことから、例え
ば、CHラジカルの385nmにおける発光ピークの強度がHラ
ジカルの655nmにおける発光ピークの少なくとも2倍の強
度となるように設定することが好ましい。Such a photocatalyst of the present invention can be produced, for example, by the following method. The photocatalyst of the present invention is a method of irradiating a substance serving as a carbon source and a substance serving as a hydrogen source with electromagnetic waves to generate CH radicals and H radicals, and exposing titanium oxide to these radicals. Is carried out in the presence of an inert gas. By performing the generation of CH radicals and H radicals in the presence of an inert gas, depending on the output of the electromagnetic wave, for example, in a microwave of 400 W, the generation of CH radicals
Plasma in which the intensity of the emission peak at 385 nm is stronger than that of the H radical at 655 nm can be obtained. The amount of inert gas is 385 nm for CH radical
And the intensity of the emission peak at 655 nm of H radicals can be determined as appropriate. Since the exposure step to the radical is preferably performed under the condition that the intensity of the emission peak at 385 nm of the CH radical is stronger than the intensity of the emission peak at 655 nm of the H radical, for example, the intensity of the emission peak at 385 nm of the CH radical is increased. It is preferable that the intensity is set to be at least twice as high as the emission peak of the H radical at 655 nm.
【００１５】炭素源となる物質は、例えば、炭化水素化
合物、一酸化炭素及び二酸化炭素からなる群から選ばれ
る少なくとも１種の物質であることができる。水素源と
なる物質は例えば、水素であることができる。不活性ガ
スは、例えば、アルゴンであることができる。さらに、
炭素源となる物質である炭化水素化合物は、例えば、メ
タン、アセチレン及びメタノールからなる群から選ばれ
る少なくとも１種の化合物であることができる。また、
炭素源となる物質、水素源となる物質及び不活性ガス
は、いずれも２種以上の物質の混合物であってもよい。
不活性ガスがアルゴンである場合、アルゴンを全ガス量
の0.1〜20容量%の範囲から選択することで、電磁波の出
力によっては、CHラジカルの385nmにおける発光ピーク
の強度をHラジカルの655nmにおける発光ピークの強度よ
り大きくすることができる。The substance serving as a carbon source can be, for example, at least one substance selected from the group consisting of hydrocarbon compounds, carbon monoxide and carbon dioxide. The substance serving as a hydrogen source can be, for example, hydrogen. The inert gas can be, for example, argon. further,
The hydrocarbon compound serving as the carbon source can be, for example, at least one compound selected from the group consisting of methane, acetylene, and methanol. Also,
Each of the substance serving as a carbon source, the substance serving as a hydrogen source, and the inert gas may be a mixture of two or more kinds of substances.
When the inert gas is argon, by selecting argon from the range of 0.1 to 20% by volume of the total gas amount, depending on the output of the electromagnetic wave, the intensity of the emission peak at 385 nm of CH radicals is increased by the emission of H radicals at 655 nm. It can be greater than the peak intensity.
【００１６】さらに、上記製造方法において、CHラジカ
ル及びHラジカルを発生させ、これらのラジカルに酸化
チタンを暴露する工程を、処理される酸化チタンの温度
が２００〜１０００℃の範囲となる条件で行うこと好ま
しい。前記ラジカルへの暴露工程は、より好ましくは、
酸化チタンの温度が４００〜９００℃の範囲となる条件
で行う。ラジカルに暴露される酸化チタンの温度によ
り、酸化チタン表面に形成される炭素系析出物の組成が
異なる。また、原料としてアナターゼ型酸化チタンを用
いた場合、７００℃を超える温度がかかると、アナター
ゼ型からルチル型に変移する。但し、この変移は、瞬時
に起こるのではなく時間とともに進行することから、７
００℃を超える温度での処理であっても処理時間によっ
ては、酸化チタンの少なくとも一部がアナターゼ型を維
持し得る。従って、酸化チタンの温度が２００〜１００
０℃の範囲、好ましくは４００〜９００℃の範囲とし、
さらには、原料としてアナターゼ型酸化チタンを用い、
酸化チタンの少なくとも一部がアナターゼ型を維持し得
る条件で、前記ラジカルへの暴露工程を行うことが好ま
しい。尚、原料となる酸化チタンは、湿式法（例えば、
硫酸法）で製造された酸化チタンや乾式法（例えば、塩
化物法）で製造された、いずれも市販の酸化チタンを用
いることができる。また、例えば、チタニウムアルコキ
シドを加水分解して生成する酸化チタンを原料として用
いることもできる。Further, in the above-mentioned production method, the step of generating CH radicals and H radicals and exposing titanium oxide to these radicals is performed under the condition that the temperature of the titanium oxide to be treated is in the range of 200 to 1000 ° C. It is preferable. The step of exposing to the radical is more preferably
This is performed under the condition that the temperature of titanium oxide is in the range of 400 to 900 ° C. The composition of the carbon-based precipitate formed on the titanium oxide surface varies depending on the temperature of the titanium oxide exposed to the radical. In addition, when anatase-type titanium oxide is used as a raw material, the temperature changes from anatase-type to rutile-type when a temperature exceeding 700 ° C. is applied. However, since this transition does not occur instantaneously but proceeds with time, 7
Even if the treatment is performed at a temperature exceeding 00 ° C., depending on the treatment time, at least a part of the titanium oxide can maintain the anatase type. Therefore, the temperature of titanium oxide is 200 to 100
0 ° C. range, preferably in the range of 400 to 900 ° C.,
Furthermore, using anatase type titanium oxide as a raw material,
It is preferable to perform the step of exposing to the radical under a condition that at least a part of the titanium oxide can maintain the anatase type. The titanium oxide as a raw material is obtained by a wet method (for example,
Titanium oxide produced by the sulfuric acid method) or commercially available titanium oxide produced by the dry method (for example, the chloride method) can be used. Further, for example, titanium oxide generated by hydrolysis of titanium alkoxide can be used as a raw material.
【００１７】本発明は、上記本発明の触媒を担体に担持
した物品を包含する。さらに、上記本発明の光触媒また
は上記物品（光触媒ユニット）を含む装置であって、前
記装置が水清浄装置、空気清浄装置、殺菌装置、脱臭装
置、照明装置、光電池、及び水の分解装置からなる群か
ら選ばれる装置を包含する。The present invention includes an article in which the above-mentioned catalyst of the present invention is supported on a carrier. Furthermore, an apparatus including the photocatalyst of the present invention or the article (photocatalyst unit), wherein the apparatus includes a water purifying device, an air purifying device, a sterilizing device, a deodorizing device, a lighting device, a photocell, and a water decomposing device. Includes devices selected from the group.
【００１８】本発明の光触媒は、例えば、基体上に担持
したととして利用できる。基体は、例えば、板状物品、
繊維、粒子であることができ、透明、半透明または不透
明であることができる。上記基板は、光触媒の使用の形
態により、種々の材質や形状を選択することができ、例
えば、樹脂製、金属製、セラミックス製あるいはガラス
製等の基板上に光触媒層を形成したユニットは、例え
ば、窓ガラスや蛍光灯に付着させることで、太陽光や蛍
光灯の光を利用して光触媒として機能することができ
る。また、基板が壁材、屋根材や床材である場合、これ
らの部材に光触媒機能を付与することもできる。The photocatalyst of the present invention can be used, for example, as supported on a substrate. The substrate is, for example, a plate-like article,
It can be a fiber, a particle, and can be transparent, translucent or opaque. The substrate can be selected from various materials and shapes depending on the mode of use of the photocatalyst.For example, a unit in which a photocatalyst layer is formed on a substrate such as a resin, a metal, a ceramic, or a glass is, for example, By attaching it to a window glass or a fluorescent lamp, it can function as a photocatalyst using sunlight or light from a fluorescent lamp. When the substrate is a wall material, a roof material, or a floor material, these members may be provided with a photocatalytic function.
【００１９】基板上への光触媒層の形成は、前記方法で
製造した光触媒を常法によりコーティングすることで行
うことができる。例えば、光触媒を必要により適当な溶
剤（例えばメタノール等）及び／又はバインダーととも
にコーティングし、次いで加熱乾燥あるいは加熱処理す
る（バインダーや溶剤使用時にはバインダーや溶剤を除
去する）ことで、本発明の光触媒ユニットを製造するこ
とができる。或いは、基板上にTiO2層を形成し、得られ
たTiO2層を有する基板表面を前記メタンと水素とアルゴ
ン等の混合ガスを用いるプラズマＣＶＤ法で処理してTi
O2層の少なくとも一部に炭素系析出物を担持させること
で、基板上への光触媒層の形成を行うこともできる。The formation of the photocatalyst layer on the substrate can be performed by coating the photocatalyst produced by the above-mentioned method by a conventional method. For example, the photocatalyst unit of the present invention can be obtained by coating a photocatalyst with an appropriate solvent (eg, methanol or the like) and / or a binder as necessary, and then heating or drying (when the binder or the solvent is used, the binder or the solvent is removed). Can be manufactured. Alternatively, a TiO 2 layer is formed on a substrate, and the surface of the obtained substrate having the TiO 2 layer is treated by a plasma CVD method using a mixed gas of methane, hydrogen, argon, etc.
By supporting the carbon-based precipitate on at least a part of the O 2 layer, a photocatalyst layer can be formed on the substrate.
【００２０】上記本発明の光触媒または光触媒ユニット
に少なくとも可視光線を含む光を照射し、この光触媒ま
たは光触媒ユニットに被分解物を接触させることで、被
分解物を分解することができる。照射する光は、可視光
線を含むものであり、例えば、可視光線以外に紫外線を
含んでいても支障はない。但し、本発明の光触媒は、可
視光線のみでも、光触媒作用を発揮する。さらに、光照
射に加えて、本発明の触媒又は本発明の光触媒ユニット
の触媒層を加熱することで、触媒機能を向上させること
もできる。加熱温度は、例えば、３０〜８０℃程度の範
囲とすることができる。The photocatalyst or photocatalyst unit of the present invention is irradiated with light containing at least visible light, and the photocatalyst or photocatalyst unit is brought into contact with the decomposed substance, whereby the decomposed substance can be decomposed. The light to be irradiated contains visible light, and for example, there is no problem even if it contains ultraviolet light in addition to visible light. However, the photocatalyst of the present invention exhibits a photocatalytic action only with visible light. Furthermore, by heating the catalyst of the present invention or the catalyst layer of the photocatalytic unit of the present invention in addition to light irradiation, the catalytic function can be improved. The heating temperature can be, for example, in the range of about 30 to 80 ° C.
【００２１】本発明の光触媒は、無機物、有機物、細
菌、微生物等のあらゆるものを可視光線を含む光を利用
して光分解することができる。The photocatalyst of the present invention is capable of photodegrading inorganic substances, organic substances, bacteria, microorganisms and the like using light containing visible light.
【００２２】特に、本発明の光触媒及び光触媒ユニット
は、特に、アセトアルデヒド、ホルムアルデヒド、たば
このヤニ、悪臭等の有機化合物の酸化・分解用として最
適である。In particular, the photocatalyst and the photocatalyst unit of the present invention are most suitable for oxidizing and decomposing organic compounds such as acetaldehyde, formaldehyde, cigarette tar, malodor and the like.
【００２３】本発明は、本発明の触媒又は本発明の光触
媒を用いた光触媒ユニットの触媒層に可視光線を含む光
を照射しつつ被分解物を接触させることを含む被分解物
の分解方法を包含する。照射する光は、可視光線を含む
ものであり、例えば、可視光線以外に紫外線を含んでい
ても支障はない。但し、本発明の光触媒は、可視光線の
みでも、光触媒作用を発揮する。さらに、光照射に加え
て、本発明の触媒又は本発明の光触媒ユニットの触媒層
を加熱することで、被分解物の光分解触媒機能を向上さ
せることもできる。加熱温度は、例えば、３０〜８０℃
程度の範囲とすることができる。The present invention provides a method for decomposing an object to be decomposed, which comprises contacting an object to be decomposed while irradiating the catalyst of the present invention or a catalyst layer of a photocatalyst unit using the photocatalyst of the present invention with light containing visible light. Include. The light to be irradiated contains visible light, and for example, there is no problem even if it contains ultraviolet light in addition to visible light. However, the photocatalyst of the present invention exhibits a photocatalytic action only with visible light. Furthermore, by heating the catalyst of the present invention or the catalyst layer of the photocatalytic unit of the present invention in addition to the light irradiation, the photocatalytic function of the decomposition target can be improved. The heating temperature is, for example, 30 to 80 ° C.
Range.
【００２４】本発明の空気の浄化方法は、少なくとも可
視光線を含む光を照射した本発明の光触媒または光触媒
ユニット（物品）に被分解物を含む空気を接触させるこ
とを特徴とする。空気が悪臭の原因物質を含む空気であ
る場合、触媒との接触により空気中に含まれる悪臭の原
因物質を分解し、悪臭を低減または除去することができ
る。また、空気が細菌を含む空気である場合、触媒との
接触により空気中に含まれる細菌の少なくとも一部を死
滅させることができる。空気が悪臭及び細菌を含む場合
には、上記作用が並行して得られることは勿論である。The method for purifying air according to the present invention is characterized in that the air containing the decomposed material is brought into contact with the photocatalyst or the photocatalyst unit (article) of the present invention irradiated with light containing at least visible light. When the air is air containing an odor-causing substance, the odor-causing substance contained in the air is decomposed by contact with the catalyst, and the odor can be reduced or eliminated. When the air is air containing bacteria, at least a part of the bacteria contained in the air can be killed by contact with the catalyst. When the air contains odors and bacteria, the above-mentioned effects can be obtained in parallel.
【００２５】本発明の水の浄化方法は、少なくとも可視
光線を含む光を照射した本発明の光触媒または光触媒ユ
ニット（物品）に被分解物を含む水を接触させることを
特徴とする。水が有機物を含有する場合、触媒との接触
により、水中の有機物を分解することができる。水が細
菌を含有する場合、触媒との接触により、水中の細菌を
死滅させることができる。水が有機物及び細菌を含む場
合には、上記作用が並行して得られることは勿論であ
る。The method for purifying water according to the present invention is characterized in that water containing decomposed substances is brought into contact with the photocatalyst or photocatalytic unit (article) of the present invention irradiated with at least light containing visible light. When water contains an organic substance, the organic substance in the water can be decomposed by contact with the catalyst. If the water contains bacteria, the bacteria in the water can be killed by contact with the catalyst. When the water contains organic matter and bacteria, the above-described effects can be obtained in parallel.
【００２６】[0026]
【実施例】以下、本発明を実施例によりさらに詳細に説
明する。 実施例１ アナターゼ型チタニア粉末（６０メッシュ以下）１０ｇ
を２００ｍｌの石英製反応管に収容した。この石英製反
応管をプラズマ発生装置に接続し、系内を真空ポンプで
排気した後、４００Ｗの電磁波（２．４５ＧＨｚ）を反
応管内のチタニア粉末に照射し、テスラーコイルによっ
てプラズマを発生させた。そして、ＣＨ4 ４．５％−Ａ
ｒ９％−Ｈ2（残部）混合ガス（流量を３０ｍｌ／分）
を系内の圧力が約１トールとなるように導入した。反応
管内のチタニア粉末を攪拌しながら３０分間処理した。
石英反応管に発生したプラズマの発光スペクトルをオー
シャンオプティクス社製（Ｓ−２０００） マルチチャ
ンネル分光システムを用いて測定した。結果を図１に示
す。比較のために、ＣＨ4４．５％−Ａｒ９％−Ｈ2（残
部）混合ガスをＣＨ4５％−Ｈ2（残部）混合ガス（流量
と圧力は同一）に変えて、同様に酸化チタンを処理し
た。そのときのプラズマの発光スペクトルを図２に示
す。図中、385nmに発光ピークを有するCHラジカル及び6
55nmに発光ピークを有するH（Ｈα）ラジカルが確認さ
れた。図１中、CHラジカルの385nmにおける発光ピーク
の強度は２４８０カウントであったのに対して、Hラジ
カルの655nmにおける発光ピークの強度は９５０カウン
トであった。また、図２中、CHラジカルの385nmにおけ
る発光ピークの強度は１０５０カウントであったのに対
して、Hラジカルの655nmにおける発光ピークの強度は１
８３０カウントであった。The present invention will be described in more detail with reference to the following examples.
I will tell. Example 1 10 g of anatase type titania powder (60 mesh or less)
Was placed in a 200 ml quartz reaction tube. This quartz anti
Connect the pipe to the plasma generator, and use a vacuum pump to
After exhausting, 400W electromagnetic wave (2.45 GHz)
Irradiate the titania powder in the tube and use a Tessler coil
To generate plasma. And CHFour 4.5% -A
r9% -HTwo(Remainder) mixed gas (flow rate 30 ml / min)
Was introduced so that the pressure in the system was about 1 Torr. reaction
The titania powder in the tube was treated for 30 minutes while stirring.
The emission spectrum of the plasma generated in the quartz
Shan Optics (S-2000) Multicha
It was measured using a tunneling spectroscopy system. The results are shown in FIG.
You. For comparison, CHFour4.5% -Ar 9% -HTwo(Remaining
Part) Mix gas to CHFour5% -HTwo(Remainder) mixed gas (flow rate
And pressure are the same) and treat titanium oxide in the same way
Was. Fig. 2 shows the emission spectrum of the plasma at that time.
You. In the figure, CH radical having an emission peak at 385 nm and 6
H (Hα) radical with emission peak at 55nm confirmed
Was. In FIG. 1, the emission peak of CH radical at 385 nm is shown.
Was 2480 counts, whereas H
Cal has an emission peak intensity at 655 nm of 950 counts.
Was. In addition, in FIG.
The intensity of the emission peak was 1050 counts,
The intensity of the emission peak at 655 nm of the H radical is 1
It was 830 counts.
【００２７】得られた試料をＸ線光電子分光装置（アル
バックファイ社製 Ｑｕａｎｔｕｍ２０００）を用いて
表面分析した。酸素、チタン及び炭素の状態分析結果を
図３、４及び５に示す。その結果得られた、酸素の１ｓ
電子（但し、感度係数は０．７３３）に帰属されるピー
クの面積は６８．７１であり、チタンの２ｐ電子（但
し、感度係数は２．０７７）に帰属されるピークの面積
は３１．２９であった。その結果、ピーク面積比（Ｏ１
ｓ／Ｔｉ２ｐ）は、２．２０であった。The surface of the obtained sample was analyzed using an X-ray photoelectron spectrometer (Quantum 2000 manufactured by ULVAC-PHI). The results of the state analysis of oxygen, titanium and carbon are shown in FIGS. The resulting 1 s of oxygen
The peak area attributed to electrons (however, the sensitivity coefficient is 0.733) is 68.71, and the peak area attributed to titanium 2p electrons (however, the sensitivity coefficient is 2.077) is 31.29. Met. As a result, the peak area ratio (O1
s / Ti2p) was 2.20.
【００２８】さらに上記試料をＴＯＦ−ＳＩＭＳ（飛行
時間型二次イオン質量分析装置）アルバックファイ社製
ＴＲＩＦＴ ＩＩを使用して表面分析した。その結果、
ＴＯＦ−ＳＩＭＳにより分析される最表面のＮａイオン
量は、４６．４％であった。Further, the surface of the sample was analyzed using a TOF-SIMS (time-of-flight secondary ion mass spectrometer) TRIFT II manufactured by ULVAC-PHI. as a result,
The amount of Na ions on the outermost surface analyzed by TOF-SIMS was 46.4%.
【００２９】アセトアルデヒドの可視光による分解試験 上記実施例１で作製した光触媒をメタノールに分散しガ
ラス板に塗布した。光触媒を塗布したガラス板をガラス
製ベルジャー型反応装置（１．９リットル）内に設置し
た。反応装置はファンを有し、系内を拡散可能とした。
光源にはハロゲンランプ（東芝ライテックＪＤＲ１１０
Ｖ ７５ＷＮ／Ｓ−ＥＫ）を用い、かつ４２０ｎｍ以下
の紫外線をカットするガラスフィルターを用いた。Decomposition test of acetaldehyde by visible light The photocatalyst prepared in Example 1 was dispersed in methanol and applied to a glass plate. The glass plate coated with the photocatalyst was placed in a glass bell jar type reactor (1.9 liter). The reactor had a fan and was able to diffuse inside the system.
The light source is a halogen lamp (Toshiba Lighting & Technology JDR110
V 75 WN / S-EK) and a glass filter that cuts ultraviolet rays of 420 nm or less was used.
【００３０】系内を十分に排気した後、アセトアルデヒ
ドを反応器内に注入して、所定濃度（1000ppm ）の反応
ガスとした。アセトアルデヒドが吸着平衡に達した後、
光照射を開始した。反応ガスは、メタナイザーに通して
からガスクロマトグラフィー（ＦＩＤ）で分析した。光
照射６０分後のアセトアルデヒド濃度は、４４０ｐｐｍ
であった。上記アセトアルデヒド分解実験を光源として
ブラックライト（岩崎電気社製Ｈ１００ＢＬ）を用い、
かつ４００ｎｍ以上の光はカットして行った。その結
果、光照射６０分後のアセトアルデヒド濃度は、８０ｐ
ｐｍであった。After the system was sufficiently evacuated, acetaldehyde was injected into the reactor to obtain a reaction gas having a predetermined concentration (1000 ppm). After the acetaldehyde reaches the adsorption equilibrium,
Light irradiation was started. The reaction gas was analyzed by gas chromatography (FID) after passing through a metanizer. The acetaldehyde concentration 60 minutes after light irradiation is 440 ppm
Met. Using a black light (Iwasaki Electric Co., H100BL) as a light source for the above acetaldehyde decomposition experiment,
Light of 400 nm or more was cut. As a result, the acetaldehyde concentration 60 minutes after light irradiation was 80 p
pm.
【００３１】実施例２ ＣＨ4 ４．５％−Ａｒ９％−Ｈ2（残部）混合ガスをＣ
Ｈ4 ４．７％−Ａｒ６％−Ｈ2（残部）混合ガスとした
以外は実施例１と同様にしてチタニア粉末を処理した。
得られるプラズマのCHラジカルの385nmにおける発光ピ
ークの強度は約１２４０カウントであったのに対して、
Hラジカルの655nmにおける発光ピークの強度は１１４０
カウントであった。Example 2 A mixed gas of CH 4 4.5% -Ar 9% -H 2 (remainder) was C
Except that the H 4 4.7% -Ar6% -H 2 ( balance) gas mixture was treated titania powder in the same manner as in Example 1.
The intensity of the emission peak at 385 nm of CH radicals in the obtained plasma was about 1240 counts,
The intensity of the emission peak at 655 nm of the H radical is 1140.
It was a count.
【００３２】得られた試料をＸ線光電子分光装置（アル
バックファイ社製 Ｑｕａｎｔｕｍ２０００）を用いて
表面分析した。酸素、チタン及び酸素のスペクトルが観
測された。その結果得られた、酸素の１ｓ電子（但し、
感度係数は０．７３３）に帰属されるピークの面積は７
０．４０であり、チタンの２ｐ電子（但し、感度係数は
２．０７７）に帰属されるピークの面積は２９．６０で
あった。その結果、ピーク面積比（Ｏ１ｓ／Ｔｉ２ｐ）
は、２．３８であった。The surface of the obtained sample was analyzed using an X-ray photoelectron spectrometer (Quantum 2000 manufactured by ULVAC-PHI). Oxygen, titanium and oxygen spectra were observed. The resulting 1s electron of oxygen (provided that
The area of the peak attributed to the sensitivity coefficient of 0.733) is 7
0.40, and the peak area attributed to 2p electrons of titanium (the sensitivity coefficient being 2.077) was 29.60. As a result, the peak area ratio (O1s / Ti2p)
Was 2.38.
【００３３】さらに上記試料をＴＯＦ−ＳＩＭＳ（飛行
時間型二次イオン質量分析装置）アルバックファイ社製
ＴＲＩＦＴ ＩＩを使用して表面分析した。その結果、
ＴＯＦ−ＳＩＭＳにより分析される最表面のＮａイオン
量は、３７．２％であった。Further, the sample was subjected to surface analysis using a TOF-SIMS (time-of-flight secondary ion mass spectrometer) TRIFT II manufactured by ULVAC-PHI. as a result,
The amount of Na ions on the outermost surface analyzed by TOF-SIMS was 37.2%.
【００３４】アセトアルデヒドの可視光による分解試験 実施例１と同様に光触媒を塗布したガラス板を作成し、
アセトアルデヒドの分解試験を行った。その結果、光源
にハロゲンランプ（東芝ライテックＪＤＲ１１０Ｖ ７
５ＷＮ／Ｓ−ＥＫ）を用い、かつ４２０ｎｍ以下の紫外
線をカットするガラスフィルターを用いた場合、光照射
６０分後のアセトアルデヒド濃度は、５１０ｐｐｍであ
った。光源としてブラックライト（岩崎電気社製Ｈ１０
０ＢＬ）を用い、かつ４００ｎｍ以上の光はカットして
行った場合、光照射６０分後のアセトアルデヒド濃度
は、８５ｐｐｍであった。上記結果から、本発明の光触
媒は、紫外線のみならず、可視光によってもアセトアル
デヒドに対する高い光分解特性を有することが分かる。Decomposition test of acetaldehyde by visible light A glass plate coated with a photocatalyst was prepared in the same manner as in Example 1,
An acetaldehyde decomposition test was performed. As a result, the light source was a halogen lamp (Toshiba Lighting & Technology JDR110V 7
When 5WN / S-EK) was used and a glass filter that cuts ultraviolet light of 420 nm or less was used, the acetaldehyde concentration after 60 minutes of light irradiation was 510 ppm. Black light (Iwasaki Electric Co. H10
0BL) and cut off light of 400 nm or more, the acetaldehyde concentration 60 minutes after light irradiation was 85 ppm. From the above results, it can be seen that the photocatalyst of the present invention has high photodegradation characteristics for acetaldehyde not only by ultraviolet light but also by visible light.
【図１】 ＣＨ4４．５％−Ａｒ９％−Ｈ2（残部）混合
ガスを用いた場合のプラズマの発光スペクトル。FIG. 1 is an emission spectrum of plasma when a mixed gas of 4.5% of CH 4, 9 % of Ar, and H 2 (remainder) is used.
【図２】 ＣＨ4５％−Ｈ2（残部）混合ガスを用いた場
合のプラズマの発光スペクトル。FIG. 2 is an emission spectrum of plasma when a mixed gas of CH 4 5% -H 2 (remainder) is used.
【図３】 実施例１で得られた試料のＸ線光電子分光法
による表面分析結果（酸素）。FIG. 3 shows the results of surface analysis (oxygen) of the sample obtained in Example 1 by X-ray photoelectron spectroscopy.
【図４】 実施例１で得られた試料のＸ線光電子分光法
による表面分析結果（チタン）。FIG. 4 is a surface analysis result (titanium) of the sample obtained in Example 1 by X-ray photoelectron spectroscopy.
【図５】 実施例１で得られた試料のＸ線光電子分光法
による表面分析結果（炭素）。FIG. 5 is a surface analysis result (carbon) of the sample obtained in Example 1 by X-ray photoelectron spectroscopy.
Claims (17)
て、Ｘ線光電子分光法により特定される酸素の１ｓ電子
（但し、感度係数は０．７３３）に帰属されるピークと
チタンの２ｐ電子（但し、感度係数は２．０７７）に帰
属されるピークの面積比（Ｏ１ｓ／Ｔｉ２ｐ）が２．４
０以下であることを特徴とする触媒。1. A photocatalyst containing titanium oxide as a main component, a peak attributed to 1s electron of oxygen (with a sensitivity coefficient of 0.733) specified by X-ray photoelectron spectroscopy, and 2p electron of titanium. (However, the area ratio (O1s / Ti2p) of the peak attributed to (the sensitivity coefficient is 2.077) is 2.4).
A catalyst characterized by being 0 or less.
ファイト、アモルファスカーボン、ダイヤモンドライク
カーボン、ダイヤモンド及び炭化水素からなる群から選
ばれる少なくとも1種の炭素系析出物を有する請求項１
に記載の光触媒。2. The method according to claim 1, wherein at least a part of the surface of the titanium oxide has at least one carbon-based precipitate selected from the group consisting of graphite, amorphous carbon, diamond-like carbon, diamond, and hydrocarbon.
The photocatalyst according to 1.
ン量が全陽イオン量の１０％以上である請求項１または
２に記載の光触媒3. The photocatalyst according to claim 1, wherein the amount of Na ions measured by TOF-SIMS is 10% or more of the total amount of cations.
ン量が全陽イオン量の２０％以上である請求項１または
２に記載の光触媒4. The photocatalyst according to claim 1, wherein the amount of Na ions measured by TOF-SIMS is 20% or more of the total amount of cations.
請求項１〜４のいずれか１項に記載の触媒。5. The catalyst according to claim 1, wherein the catalyst has substantially no support of titanium carbide.
項１〜５のいずれか１項に記載の光触媒。6. The photocatalyst according to claim 1, which has visible light activity and ultraviolet light activity.
クライト光照射下における光触媒活性を１００とした場
合、４２０ｎｍ以下の光をカットしたハロゲンランプ光
照射下における光触媒活性が少なくとも１０である請求
項１〜５のいずれか１項に記載の光触媒。7. The photocatalytic activity under irradiation of a halogen lamp which cuts light of 420 nm or less is at least 10, assuming that the photocatalytic activity under irradiation of black light which cuts light of 400 nm or more is 100. 6. The photocatalyst according to any one of 5.
請求項１〜７のいずれか１項に記載の触媒に被分解物を
接触させることを特徴とする物質の分解方法。8. A method for decomposing a substance, comprising: bringing a substance to be decomposed into contact with the catalyst according to claim 1, which is irradiated with light containing at least visible light.
は微生物である請求項８に記載の方法。9. The method according to claim 8, wherein the substance to be decomposed is an inorganic substance, an organic substance, a bacterium or a microorganism.
た請求項１〜７のいずれか１項に記載の触媒に被分解物
を含む空気を接触させることを特徴とする空気の浄化方
法。10. A method for purifying air, comprising contacting air containing decomposed substances with the catalyst according to claim 1, which is irradiated with light containing at least visible light.
の接触により悪臭を低減または除去する請求項１０に記
載の空気の浄化方法。11. The air purification method according to claim 10, wherein the air is air containing a bad odor, and the bad odor is reduced or removed by contact with a catalyst.
の接触により細菌の少なくとも一部を死滅させる請求項
１０に記載の空気の浄化方法。12. The method for purifying air according to claim 10, wherein the air is air containing bacteria, and at least a part of the bacteria is killed by contact with the catalyst.
た請求項１〜７のいずれか１項に記載の触媒に被分解物
を含む水を接触させることを特徴とする水の浄化方法。13. A method for purifying water, comprising contacting water containing decomposed substances with the catalyst according to claim 1, which is irradiated with light containing at least visible light.
より、水中の有機物を分解する請求項１３に記載の水の
浄化方法。14. The water purification method according to claim 13, wherein the water contains an organic substance, and the organic substance in the water is decomposed by contact with the catalyst.
り、水中の細菌の少なくとも一部を死滅させる請求項１
３に記載の水の浄化方法。15. The water according to claim 1, wherein the water contains bacteria, and the contact with the catalyst kills at least a part of the bacteria in the water.
3. The method for purifying water according to 3.
触媒を担体に担持したことを特徴とする物品。16. An article, characterized in that the catalyst according to claim 1 is supported on a carrier.
触媒または請求項１６に記載の物品を含む装置であっ
て、前記装置が水清浄装置、空気清浄装置、殺菌装置、
脱臭装置、照明装置、光電池、及び水の分解装置からな
る群から選ばれることを特徴とする装置。17. An apparatus comprising the catalyst according to any one of claims 1 to 7 or the article according to claim 16, wherein the apparatus is a water purifier, an air purifier, a sterilizer,
A device selected from the group consisting of a deodorizing device, a lighting device, a photocell, and a water decomposing device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14198398A JP3962770B2 (en) | 1998-05-22 | 1998-05-22 | Photocatalyst having visible light activity and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14198398A JP3962770B2 (en) | 1998-05-22 | 1998-05-22 | Photocatalyst having visible light activity and use thereof |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002374858A Division JP2003260370A (en) | 2002-12-25 | 2002-12-25 | Photocatalyst having visible ray activity and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11333301A true JPH11333301A (en) | 1999-12-07 |
| JP3962770B2 JP3962770B2 (en) | 2007-08-22 |
Family
ID=15304678
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001098219A (en) * | 1999-09-28 | 2001-04-10 | Agency Of Ind Science & Technol | Photocatalyst coating for removal of nitrogen oxide in air and article having the coating |
| US6627579B1 (en) | 1999-06-30 | 2003-09-30 | Sumitomo Chemical Company, Limited | Titanium oxide, photocatalyst comprising same and photocatalytic coating agent |
-
1998
- 1998-05-22 JP JP14198398A patent/JP3962770B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6627579B1 (en) | 1999-06-30 | 2003-09-30 | Sumitomo Chemical Company, Limited | Titanium oxide, photocatalyst comprising same and photocatalytic coating agent |
| JP2001098219A (en) * | 1999-09-28 | 2001-04-10 | Agency Of Ind Science & Technol | Photocatalyst coating for removal of nitrogen oxide in air and article having the coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3962770B2 (en) | 2007-08-22 |
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