JPH11253818A - Photocatalyst and photocatalytic device - Google Patents
Photocatalyst and photocatalytic deviceInfo
- Publication number
- JPH11253818A JPH11253818A JP10063581A JP6358198A JPH11253818A JP H11253818 A JPH11253818 A JP H11253818A JP 10063581 A JP10063581 A JP 10063581A JP 6358198 A JP6358198 A JP 6358198A JP H11253818 A JPH11253818 A JP H11253818A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- alloy
- particles
- semiconductor
- platinum
- 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.)
- Withdrawn
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 105
- 230000001699 photocatalysis Effects 0.000 title description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000004065 semiconductor Substances 0.000 claims abstract description 42
- 239000010931 gold Substances 0.000 claims abstract description 29
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 25
- 229910052737 gold Inorganic materials 0.000 claims abstract description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010419 fine particle Substances 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 5
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 35
- 239000000956 alloy Substances 0.000 abstract description 35
- 239000002131 composite material Substances 0.000 abstract description 33
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract 4
- -1 and for example Substances 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 22
- 239000000843 powder Substances 0.000 description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910001020 Au alloy Inorganic materials 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 238000004887 air purification Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒および光触
媒装置に関する。[0001] The present invention relates to a photocatalyst and a photocatalyst device.
【０００２】[0002]
【従来の技術】光触媒は、高温を必要とせず常温で光励
起により触媒作用を発現するので、吸着材と組み合わせ
て脱臭フィルターその他の空気浄化フィルター等として
利用されている。従来知られている実用的な光触媒とし
ては、酸化チタン（ＴｉＯ2)、硫化カドミウム（Ｃｄ
Ｓ）、チタン酸ストロンチウム（ＳｒＴｉＯ3)、チタン
酸カリウム（Ｋ2 Ｔｉ6 Ｏ13）、酸化タンタル（Ｔａ2
Ｏ5 ）等がある。これらはいずれも半導体であり、少な
くとも実用分野において他の材質の光触媒はこれまでに
知られていない。2. Description of the Related Art A photocatalyst exhibits a catalytic action by photoexcitation at room temperature without requiring a high temperature, and is used in combination with an adsorbent as a deodorizing filter or another air purification filter. Conventionally known practical photocatalysts include titanium oxide (TiO 2 ), cadmium sulfide (Cd
S), strontium titanate (SrTiO 3 ), potassium titanate (K 2 Ti 6 O 13 ), tantalum oxide (Ta 2
O 5 ). These are all semiconductors, and photocatalysts of other materials have not been known at least in the practical field.
【０００３】また、半導体光触媒として代表的な酸化チ
タンは特開平１−１８９３２２号公報に開示されてい
る。酸化チタン光触媒を用いた脱臭フィルター等の空気
浄化器では、吸着性能を向上させるために活性炭との併
用を行っており（特開平８−３３２３７８号公報）、酸
化チタンの触媒能力を向上させるためにその電荷分離を
行うためにＰｄ等の金属を担持させる方法が考えられて
いる（特開平１−２１８６３５号公報）。A typical titanium oxide as a semiconductor photocatalyst is disclosed in JP-A-1-189322. An air purifier such as a deodorizing filter using a titanium oxide photocatalyst is used in combination with activated carbon in order to improve the adsorption performance (Japanese Patent Laid-Open No. 8-332378). In order to perform the charge separation, a method of supporting a metal such as Pd has been considered (Japanese Patent Application Laid-Open No. 1-218635).
【０００４】このような従来の種々の要請および改良に
対して、従来の半導体光触媒に比べて更に高い触媒能力
を有する光触媒が開発されれば実用上極めて有用であ
る。[0004] In response to such various conventional demands and improvements, it is practically useful if a photocatalyst having a higher catalytic ability than conventional semiconductor photocatalysts is developed.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、従来
の半導体光触媒以外の材質の光触媒およびこの光触媒を
利用し従来の半導体光触媒よりも高い触媒能力を有する
光触媒を提供すると共に、これらの光触媒を利用した光
触媒装置を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a photocatalyst made of a material other than the conventional semiconductor photocatalyst, a photocatalyst utilizing the photocatalyst, and having a higher catalytic ability than the conventional semiconductor photocatalyst. It is an object of the present invention to provide a photocatalyst device utilizing the same.
【０００６】[0006]
【課題を解決するための手段】本発明の第一の観点によ
れば、半導体光触媒以外の材質の新規な光触媒として、
白金上に金の微粒子を担持したことを特徴とする光触媒
が提供される。また、本発明の第二の観点によれば、従
来の半導体光触媒よりも高い触媒能力を有する光触媒と
して、白金上に金の微粒子を担持し、該白金を更に半導
体光触媒上に担持したことを特徴とする光触媒が提供さ
れる。この半導体光触媒は、典型的には酸化チタン（Ｔ
ｉＯ2)、硫化カドミウム（ＣｄＳ）、チタン酸ストロン
チウム（ＳｒＴｉＯ3)、チタン酸カリウム（Ｋ2 Ｔｉ6
Ｏ13）、酸化タンタル（Ｔａ2 Ｏ5 ）から成る群から選
択される。ただし、上記以外の半導体光触媒を用いるこ
ともできる。According to a first aspect of the present invention, a novel photocatalyst of a material other than a semiconductor photocatalyst is provided.
There is provided a photocatalyst characterized by carrying fine particles of gold on platinum. According to a second aspect of the present invention, as a photocatalyst having a higher catalytic ability than a conventional semiconductor photocatalyst, gold fine particles are supported on platinum, and the platinum is further supported on the semiconductor photocatalyst. Is provided. This semiconductor photocatalyst is typically titanium oxide (T
iO 2 ), cadmium sulfide (CdS), strontium titanate (SrTiO 3 ), potassium titanate (K 2 Ti 6
O 13 ) and tantalum oxide (Ta 2 O 5 ). However, a semiconductor photocatalyst other than the above can also be used.
【０００７】更に、本発明の第三の観点によれば、上記
第一または第二の観点による光触媒のいずれかと、該光
触媒への光照射手段とを備えたことを特徴とする光触媒
装置が提供される。Further, according to a third aspect of the present invention, there is provided a photocatalyst device comprising: one of the photocatalysts according to the first or second aspect; and means for irradiating the photocatalyst with light. Is done.
【０００８】[0008]
【発明の実施の形態】本発明の第一観点による光触媒
は、白金に金の微粒子を担持したもの（以下、本明細書
中ではこれを「合金」と呼称する）に紫外線を照射する
と触媒作用を発現するという新規な知見に基づく合金光
触媒である。ここで一般に、白金の形態は表面積の大き
い微細な粒子状であることが触媒として望ましく、例え
ば粒径が１０ｎｍあるいはそれ以下のものが従来公知の
製法により得られる。BEST MODE FOR CARRYING OUT THE INVENTION A photocatalyst according to the first aspect of the present invention has a catalytic action when ultraviolet light is irradiated on a platinum-supported gold fine particle (hereinafter referred to as “alloy” in the present specification). It is an alloy photocatalyst based on a novel finding that the compound expresses. Here, in general, it is desirable that the form of platinum is a fine particle having a large surface area as a catalyst.
【０００９】金の微粒子は、上記白金粒子の表面に担持
されるために、白金粒子よりも更に微細な粒子であり、
典型的には粒径が数ｎｍあるいはそれ以下であることが
望ましい。製法は特に限定する必要はなく、従来公知の
製法でよい。白金上に金の微粒子を担持させた合金が光
触媒作用を発現するメカニズムは、現時点では必ずしも
完全に解明されてはいないが、以下のように推察され
る。The fine gold particles are finer particles than the platinum particles because they are carried on the surface of the platinum particles.
Typically, it is desirable that the particle size is several nm or less. The production method need not be particularly limited, and may be a conventionally known production method. The mechanism by which an alloy of gold particles supported on platinum exhibits a photocatalytic action has not been completely elucidated at the present time, but is presumed as follows.
【００１０】白金上に金の微粒子を均一に少量分散担持
することにより、触媒上が疎水状態となり臭気物質が担
持しない場合と比較してより吸着する。次に、金が微粒
子で均一に白金上に担持されたことにより、紫外線等の
エネルギーにより、金が活性化し、金から白金への電荷
の移動が起こり、白金の触媒活性が生じ、白金を高温
（２００℃）にしたと同様の効果が生じた若しくは、白
金と金の複合化した成分が紫外線により触媒効果を生じ
たと考えられる。[0010] By uniformly dispersing and supporting a small amount of fine gold particles on platinum, the catalyst becomes hydrophobic and adsorbs more than when no odorant is supported. Next, the gold is uniformly supported on the platinum in fine particles, so that the gold and the like are activated by the energy of ultraviolet rays and the like, and the electric charge is transferred from the gold to the platinum. (200 ° C.), it is considered that the same effect was produced, or the composite component of platinum and gold produced a catalytic effect by ultraviolet rays.
【００１１】更に、本発明の第二観点による光触媒は、
上記第一観点による合金光触媒を従来の半導体光触媒上
に担持させることにより、担持基材である半導体光触媒
よりも格段に高い触媒能力を発現するという新規な知見
に基づく合金・半導体複合光触媒である。合金光触媒を
半導体光触媒上に担持させた合金・半導体複合光触媒が
担持基材である半導体光触媒に比べて格段に高い光触媒
能力を発揮するメカニズムは、現時点では必ずしも完全
に解明されてはいないが、以下のように推察される。Further, the photocatalyst according to the second aspect of the present invention comprises:
An alloy / semiconductor composite photocatalyst based on a novel finding that, by supporting the alloy photocatalyst according to the first aspect on a conventional semiconductor photocatalyst, a significantly higher catalytic ability is exhibited than the semiconductor photocatalyst as a supporting base material. The mechanism by which an alloy / semiconductor composite photocatalyst in which an alloy photocatalyst is supported on a semiconductor photocatalyst exhibits a much higher photocatalytic ability than the semiconductor photocatalyst which is a supporting base material is not necessarily completely elucidated at the present time, but is described below. It is inferred as follows.
【００１２】すなわち、メカニズムとしては上記の理由
の他に以下の点が考えられる。 ・白金上に金が担持されたことにより酸化チタンより白
金に電荷が移動する電荷分離の割合が向上し触媒特性が
向上した。 ・金により白金の被害が防止され、白金上で生じる還元
作用の効率が向上することにより、酸化チタン上で生じ
る酸化作用による浄化の向上が得られたと考えられる。That is, the following points can be considered as a mechanism in addition to the above reasons. -Since gold was carried on platinum, the ratio of charge separation in which charges were transferred from titanium oxide to platinum was improved, and the catalytic properties were improved. -It is considered that the damage of platinum was prevented by gold, and the efficiency of the reduction action generated on platinum was improved, thereby improving the purification by the oxidation action generated on titanium oxide.
【００１３】上記第一観点による合金光触媒または第二
観点による合金・半導体複合光触媒と、この光触媒に光
を照射する手段とを組み合わせることにより、例えば脱
臭フィルターのような空気浄化フィルター等に適した光
触媒装置が提供される。以下、実施例により本発明を更
に具体的に説明する。By combining the alloy photocatalyst according to the first aspect or the alloy / semiconductor composite photocatalyst according to the second aspect with means for irradiating the photocatalyst with light, a photocatalyst suitable for an air purifying filter such as a deodorizing filter, for example. An apparatus is provided. Hereinafter, the present invention will be described more specifically with reference to examples.
【００１４】[0014]
【実施例】〔実施例１〕本発明の第一観点によるＰｔ−
Ａｕ合金光触媒を以下の手順で製造した。 Ｐｔ／Ａｌ2 Ｏ3 複合粉末の作成 Ｐｔ（ＮＯ2)2(ＮＨ3)2 を２．３９wt％含有する水溶液
に、触媒担持基材としてのγ−Ａｌ2 Ｏ3 粉末（平均粒
径１０μｍ）を添加して３時間攪拌した。[Embodiment 1] Pt- according to the first aspect of the present invention.
An Au alloy photocatalyst was produced by the following procedure. Preparation of Pt / Al 2 O 3 composite powder γ-Al 2 O 3 powder (average particle size: 10 μm) as a catalyst supporting base material in an aqueous solution containing 2.39 wt% of Pt (NO 2 ) 2 (NH 3 ) 2 Was added and stirred for 3 hours.
【００１５】濾過により固形分を採取し、大気中で１２
０℃×２４時間の乾燥処理を行った後、大気中で３００
℃×２時間の熱処理を施した。これにより、Ａｌ2 Ｏ3
粒子の表面にＰｔ粒子が担持されたＰｔ／Ａｌ2 Ｏ3複
合粉末が得られた。この複合粉末のＰｔ含有量は１．９
０wt％であった。またＡｌ2 Ｏ3 粒子上に担持されてい
るＰｔ粒子は粒径２〜３ｎｍであった。The solid content is collected by filtration,
After performing a drying treatment at 0 ° C. for 24 hours, the drying treatment was performed in the air for 300 hours.
Heat treatment was performed at 2 ° C. × 2 hours. Thereby, Al 2 O 3
A Pt / Al 2 O 3 composite powder having Pt particles supported on the surface of the particles was obtained. The Pt content of this composite powder was 1.9.
It was 0 wt%. The Pt particles carried on the Al 2 O 3 particles had a particle size of 2 to 3 nm.
【００１６】 〔Ｐｔ−Ａｕ〕／Ａｌ2 Ｏ3 複合粉末
の作成 上記Ｐｔ／Ａｌ2 Ｏ3 複合粉末を９．０１wt％含有する
６０℃のイオン交換水に、下記成分を順次添加した。
（ ）内は添加量であり、全てを添加後の混合液全体の
重量を基準として表示した。 ＨＡｕＣｌ4 ・４Ｈ2 Ｏ（１．９８×１０-2wt％） Ｎａ2 Ｓ2 Ｏ3 ・５Ｈ2 Ｏ（８．９８×１０-2wt％） Ｎａ2 ＳＯ4 ・（２．３０×１０-1wt％） Ｃ6 Ｈ7 ＮａＯ6 ・Ｈ2 Ｏ（９．０３×１０-1wt％） 得られた混合液をｐＨ７．５９に調整し、２４時間攪拌
して、Ｐｔ上にＡｕを還元析出させた。Preparation of [Pt-Au] / Al 2 O 3 Composite Powder The following components were sequentially added to ion exchange water at 60 ° C. containing 9.01 wt% of the above Pt / Al 2 O 3 composite powder.
The amount in parentheses is the amount of addition, which is shown based on the weight of the whole mixed solution after the addition. HAuCl 4 · 4H 2 O (1.98 × 10 -2 wt%) Na 2 S 2 O 3 · 5H 2 O (8.98 × 10 -2 wt%) Na 2 SO 4 · (2.30 × 10 - 1 wt%) C 6 H 7 NaO 6 .H 2 O (9.03 × 10 -1 wt%) The obtained mixture was adjusted to pH 7.59, stirred for 24 hours, and reduced Au on Pt. Was deposited.
【００１７】濾過により固形分を採取し、６０℃のイオ
ン交換水で洗浄してから、大気中で１２０℃×２時間の
乾燥処理を行った後、大気中で５００℃×２時間の熱処
理を施した。これにより、Ａｌ2 Ｏ3 粒子に担持された
Ｐｔ粒子上に更にＡｕ粒子が担持された〔Ｐｔ−Ａｕ〕
／Ａｌ2 Ｏ3 複合粉末が得られた。この複合粉末は、Ｐ
ｔ−Ａｕ合金光触媒がＡｌ2 Ｏ3 基材上に担持されたも
のであり、模式的には図１に示したような構造である。
Ｐｔ−Ａｕ合金中のＰｔとＡｕとの重量比はＰｔ：Ａｕ
＝１９：１であり、複合粉末全体のＰｔとＡｕの合計含
有量は２wt％であった。またＡｌ2 Ｏ3 粒子上に担持さ
れているＰｔ−Ａｕ合金粒子は粒径２〜３ｎｍであっ
た。The solid content is collected by filtration, washed with ion-exchanged water at 60 ° C., dried in air at 120 ° C. for 2 hours, and then heat-treated in air at 500 ° C. for 2 hours. gave. As a result, Au particles were further supported on the Pt particles supported on the Al 2 O 3 particles [Pt-Au].
/ Al 2 O 3 composite powder was obtained. This composite powder is
The t-Au alloy photocatalyst is supported on an Al 2 O 3 substrate, and has a structure as schematically shown in FIG.
The weight ratio of Pt to Au in the Pt-Au alloy is Pt: Au.
= 19: 1, and the total content of Pt and Au in the entire composite powder was 2% by weight. The Pt-Au alloy particles supported on the Al2O3 particles had a particle size of 2 to 3 nm.
【００１８】なお、上記のＰｔ粒径およびＰｔ−Ａｕ粒
径の測定は透過電子顕微鏡（ＴＥＭ）により、また組成
分析は蛍光Ｘ線分析により行った。得られたＰｔ−Ａｕ
合金光触媒の光触媒効果を評価するために、下記条件に
てアセトアルデヒド除去試験を行った。 〔試験条件〕 Ｐｔ−Ａｕ担持量：１ｇ 担持体：アルミニウム 浄化対象：１０リットルガスパック アセトアルデヒド
１００ｐｐｍ 紫外線照射量：０．７ｍＷ／ｃｍ2 比較のために、紫外線照射なし（暗吸着）の場合とＰｔ
単独で紫外線照射ありの場合についても同様の試験を行
った。The measurement of the Pt particle size and the Pt-Au particle size was performed by a transmission electron microscope (TEM), and the composition analysis was performed by X-ray fluorescence analysis. Pt-Au obtained
An acetaldehyde removal test was performed under the following conditions to evaluate the photocatalytic effect of the alloy photocatalyst. [Test conditions] Pt-Au carrying amount: 1 g Carrier: Aluminum Purification target: 10 liter gas pack Acetaldehyde 100 ppm UV irradiation amount: 0.7 mW / cm 2 For comparison, the case without UV irradiation (dark adsorption) and the case with Pt were used.
The same test was carried out for the case where there was ultraviolet irradiation alone.
【００１９】その結果、図２に示すように、いずれの場
合も試験時間の増加に伴って除去率は増加しているが、
本発明によるＰｔ−Ａｕ合金光触媒は他の２つの場合に
比べて格段に高い除去率が得られており、光触媒作用の
発現が明確に認められる。 〔実施例２〕本発明の第二観点による〔Ｐｔ−Ａｕ〕Ｔ
ｉＯ2 合金・半導体複合光触媒を以下の手順で製造し
た。As a result, as shown in FIG. 2, in each case, the removal rate increases with an increase in the test time.
The Pt-Au alloy photocatalyst according to the present invention has a remarkably high removal rate as compared with the other two cases, and the manifestation of the photocatalytic action is clearly recognized. [Example 2] [Pt-Au] T according to the second aspect of the present invention
An iO 2 alloy / semiconductor composite photocatalyst was produced by the following procedure.
【００２０】 Ｐｔ／ＴｉＯ2 複合粉末の作成 Ｐｔ（ＮＯ2)2(ＮＨ3)2 を２．３９wt％含有する水溶液
に、半導体光触媒としてのＴｉＯ2 粉末（平均粒径５μ
ｍ）を添加して３時間攪拌した。濾過により固形分を採
取し、大気中で１２０℃×２４時間の乾燥処理を行った
後、大気中で３００℃×２時間の熱処理を施した。Preparation of Pt / TiO 2 Composite Powder In an aqueous solution containing 2.39 wt% of Pt (NO 2 ) 2 (NH 3 ) 2 , TiO 2 powder (average particle size 5 μm) as a semiconductor photocatalyst was added.
m) was added and stirred for 3 hours. A solid content was collected by filtration, dried at 120 ° C. for 24 hours in the air, and then heat-treated at 300 ° C. for 2 hours in the air.
【００２１】これにより、ＴｉＯ2 粒子の表面にＰｔ粒
子が担持されたＰｔ／ＴｉＯ2 複合粉末が得られた。こ
の複合粉末のＰｔ含有量は１．９０wt％であった。また
ＴｉＯ2 粒子上に担持されているＰｔ粒子は粒径２〜３
ｎｍであった。 〔Ｐｔ−Ａｕ〕／ＴｉＯ2 複合粉末の作成 上記Ｐｔ／ＴｉＯ2 複合粉末を９．０１wt％含有する６
０℃のイオン交換水に、下記成分を順次添加した。
（ ）内は添加量であり、全てを添加後の混合液全体の
重量を基準として表示した。As a result, a Pt / TiO 2 composite powder having Pt particles supported on the surface of TiO 2 particles was obtained. The Pt content of this composite powder was 1.90 wt%. The Pt particles supported on the TiO 2 particles have a particle size of 2-3.
nm. Preparation of [Pt-Au] / TiO 2 composite powder 6 containing 9.01 wt% of the above Pt / TiO 2 composite powder
The following components were sequentially added to ion-exchanged water at 0 ° C.
The amount in parentheses is the amount of addition, which is shown based on the weight of the whole mixed solution after the addition.
【００２２】 ＨＡｕＣｌ4 ・４Ｈ2 Ｏ（１．９８×１０-2wt％） Ｎａ2 Ｓ2 Ｏ3 ・５Ｈ2 Ｏ（８．９８×１０-2wt％） Ｎａ2 ＳＯ4 ・（２．３０×１０-1wt％） Ｃ6 Ｈ7 ＮａＯ6 ・Ｈ2 Ｏ（９．０３×１０-1wt％） 得られた混合液をｐＨ７．５９に調整し、２４時間攪拌
して、Ｐｔ上にＡｕを還元析出させた。[0022] HAuCl 4 · 4H 2 O (1.98 × 10 -2 wt%) Na 2 S 2 O 3 · 5H 2 O (8.98 × 10 -2 wt%) Na 2 SO 4 · (2.30 (× 10 -1 wt%) C 6 H 7 NaO 6 .H 2 O (9.03 × 10 -1 wt%) The obtained mixture was adjusted to pH 7.59, stirred for 24 hours, and placed on Pt. Au was precipitated by reduction.
【００２３】濾過により固形分を採取し、６０℃のイオ
ン交換水で洗浄してから、大気中で１２０℃×２時間の
乾燥処理を行った後、大気中で５００℃×２時間の熱処
理を施した。これにより、ＴｉＯ2 粒子に担持されたＰ
ｔ粒子上に更にＡｕ粒子が担持された〔Ｐｔ−Ａｕ〕／
ＴｉＯ2 複合粉末が得られた。この複合粉末は、Ｐｔ−
Ａｕ合金光触媒がＴｉＯ2 半導体光触媒上に担持された
ものであり、模式的には図３に示したような構造であ
る。Ｐｔ−Ａｕ合金中のＰｔとＡｕとの重量比はＰｔ：
Ａｕ＝１９：１であり、複合粉末全体のＰｔとＡｕの合
計含有量は２wt％であった。またＴｉＯ2 粒子上に担持
されているＰｔ−Ａｕ合金粒子は粒径２〜３ｎｍであっ
た。A solid content is collected by filtration, washed with ion-exchanged water at 60 ° C., dried in air at 120 ° C. for 2 hours, and then heat-treated at 500 ° C. in air for 2 hours. gave. Thereby, the P supported on the TiO 2 particles
Au particles further supported on the t particles [Pt-Au] /
A TiO 2 composite powder was obtained. This composite powder is Pt-
An Au alloy photocatalyst is supported on a TiO 2 semiconductor photocatalyst, and has a structure as schematically shown in FIG. The weight ratio of Pt to Au in the Pt-Au alloy is Pt:
Au = 19: 1, and the total content of Pt and Au in the entire composite powder was 2% by weight. The Pt—Au alloy particles supported on the TiO 2 particles had a particle size of 2 to 3 nm.
【００２４】なお、上記のＰｔ粒径およびＰｔ−Ａｕ粒
径の測定は透過電子顕微鏡（ＴＥＭ）により、また組成
分析は蛍光Ｘ線分析により行った。得られた〔Ｐｔ−Ａ
ｕ〕ＴｉＯ2 合金・半導体複合光触媒の光触媒効果を評
価するために、下記条件にてアンモニア除去試験を行っ
た。 〔試験条件〕 Ｐｔ−Ａｕ担持量：０．１ｇ 担持体：アルミニウム 浄化対象：１０リットルガスパック アンモニア１００
ｐｐｍ 紫外線照射量：０．７ｍＷ／ｃｍ2 比較のために、ＴｉＯ2 単独の場合についても同様の試
験を行った。The Pt particle size and the Pt-Au particle size were measured by a transmission electron microscope (TEM), and the composition analysis was performed by X-ray fluorescence analysis. The obtained [Pt-A
u] In order to evaluate the photocatalytic effect of the TiO 2 alloy / semiconductor composite photocatalyst, an ammonia removal test was performed under the following conditions. [Test conditions] Pt-Au carrying amount: 0.1 g Carrier: aluminum Purification target: 10 liter gas pack ammonia 100
ppm Ultraviolet irradiation amount: 0.7 mW / cm 2 For comparison, the same test was performed for TiO 2 alone.
【００２５】その結果、図４に示すように、いずれの場
合も試験時間の増加に伴って除去率は増加しているが、
本発明による〔Ｐｔ−Ａｕ〕／ＴｉＯ2 合金・半導体複
合光触媒はＴｉＯ2 半導体光触媒に比べて飛躍的に高い
除去率が得られている。典型的には、本発明の〔Ｐｔ−
Ａｕ〕／ＴｉＯ2 合金・半導体複合光触媒では試験時間
１００分でアンモニア除去率はほぼ１００％に達してい
る。As a result, as shown in FIG. 4, in each case, the removal rate increases as the test time increases.
The [Pt-Au] / TiO 2 alloy / semiconductor composite photocatalyst according to the present invention has a remarkably higher removal rate than the TiO 2 semiconductor photocatalyst. Typically, the [Pt-
In the case of the Au] / TiO 2 alloy / semiconductor composite photocatalyst, the ammonia removal rate reached almost 100% in 100 minutes of the test time.
【００２６】これに対して、その時点での従来のＴｉＯ
2 半導体光触媒の除去率は２０％程度であり、しかも増
加がほぼ飽和した状態になっていて、それ以上試験時間
をかけても除去率の増加は殆ど期待できない。以上の実
施例１および実施例２にて得られた合金光触媒および合
金・半導体複合光触媒の浄化能力を、従来のＴｉＯ2 光
触媒および活性炭吸着材＋ＴｉＯ2 光触媒とを比較評価
するために、実施例２と同様の条件でアンモニア除去試
験を行った。On the other hand, the conventional TiO
(2) The removal rate of the semiconductor photocatalyst is about 20%, and the increase is almost saturated, and the increase in the removal rate can hardly be expected even if the test time is further extended. Example 2 was used to compare and evaluate the purifying ability of the alloy photocatalyst and the alloy / semiconductor composite photocatalyst obtained in the above Examples 1 and 2 with the conventional TiO 2 photocatalyst and activated carbon adsorbent + TiO 2 photocatalyst. An ammonia removal test was performed under the same conditions as described above.
【００２７】その結果、図５に示すように、本発明第一
観点によるＰｔ−Ａｕ合金光触媒は明瞭に光触媒作用を
発現し、また本発明第二観点による〔Ｐｔ−Ａｕ〕／Ｔ
ｉＯ 2 合金・半導体複合光触媒は試験時間１００分以降
の定常状態で従来のＴｉＯ2光触媒の約４倍、従来の活
性炭吸着材＋ＴｉＯ2 光触媒の約３倍の浄化能力を発揮
した。As a result, as shown in FIG.
Pt-Au alloy photocatalyst from the viewpoint clearly has photocatalytic action
[Pt-Au] / T according to the second aspect of the present invention
iO TwoFor alloy / semiconductor composite photocatalyst after 100 minutes test time
In the steady state of conventional TiOTwoAbout 4 times the photocatalyst,
Charcoal adsorbent + TiOTwoDemonstrate about three times the purification capacity of photocatalyst
did.
【００２８】〔実施例３〕本発明の第三観点により、Ｐ
ｔ−Ａｕ合金光触媒を用いた光触媒装置を以下の手順で
作製した。実施例１で製造したＰｔ−Ａｕ合金光触媒粉
末をアルミナゾルと混合した後、アルミニウムハニカム
にディッピングにより塗布し、２５０〜５００℃の温度
で焼き付けて光触媒フィルターを作製した。Embodiment 3 According to a third aspect of the present invention, P
A photocatalyst device using a t-Au alloy photocatalyst was manufactured in the following procedure. After mixing the Pt-Au alloy photocatalyst powder produced in Example 1 with alumina sol, it was applied to an aluminum honeycomb by dipping and baked at a temperature of 250 to 500 ° C. to produce a photocatalytic filter.
【００２９】次に、この光触媒フィルターと紫外線ラン
プとを搭載した空気浄化器を作製した。 〔実施例４〕本発明の第三観点により、〔Ｐｔ−Ａｕ〕
ＴｉＯ2 合金・半導体複合光触媒を用いた光触媒装置を
以下の手順で作製した。Next, an air purifier equipped with the photocatalyst filter and the ultraviolet lamp was manufactured. Example 4 According to the third aspect of the present invention, [Pt-Au]
A photocatalyst device using a TiO 2 alloy / semiconductor composite photocatalyst was manufactured in the following procedure.
【００３０】実施例２で製造した〔Ｐｔ−Ａｕ〕ＴｉＯ
2 合金・半導体複合光触媒粉末をアルミニウムハニカム
にディッピングにより塗布し、２５０〜５００℃の温度
で焼き付けて光触媒フィルターを作製した。次に、この
光触媒フィルターと紫外線ランプとを搭載した空気浄化
器を作製した。[Pt-Au] TiO manufactured in Example 2
The two- alloy / semiconductor composite photocatalyst powder was applied to an aluminum honeycomb by dipping and baked at a temperature of 250 to 500 ° C. to produce a photocatalytic filter. Next, an air purifier equipped with the photocatalyst filter and the ultraviolet lamp was manufactured.
【００３１】[0031]
【発明の効果】以上説明したように、本発明によれば、
従来の半導体光触媒に対して全く新規な材質であるＰｔ
−Ａｕ合金光触媒およびこの合金光触媒を利用し従来の
半導体光触媒よりも飛躍的に高い触媒能力を有する合金
・半導体複合光触媒が提供されると共に、これらの光触
媒を利用した光触媒装置も提供される。As described above, according to the present invention,
Pt, a completely new material for conventional semiconductor photocatalysts
An Au-alloy photocatalyst and an alloy / semiconductor composite photocatalyst utilizing the alloy photocatalyst and having a remarkably higher catalytic ability than a conventional semiconductor photocatalyst are provided, and a photocatalyst device using these photocatalysts is also provided.
【００３２】本発明の光触媒および光触媒装置は、特に
自動車などの車室用空気浄化器等に適用した場合、通常
の脱臭作用を発揮するばかりでなく、外部から進入する
ＮＯ x 、ＳＯx に対してもＰｔの触媒作用により除去作
用を発揮するという副次的な効果も得られる。The photocatalyst and photocatalyst device of the present invention are
When applied to air purifiers for cabin of automobiles, etc.
Not only deodorizes but also enters from outside
NO x, SOxIs removed by the catalytic action of Pt
There is also a secondary effect of exerting an effect.
【図１】図１は、本発明第一観点によるＰｔ−Ａｕ合金
光触媒と担持体アルミナ粒子とから成る構造を示す概念
図である。FIG. 1 is a conceptual diagram showing a structure including a Pt—Au alloy photocatalyst and alumina particles on a carrier according to a first aspect of the present invention.
【図２】図２は、本発明第一観点によるＰｔ−Ａｕ合金
光触媒の光触媒触媒作用の発現を示すグラフである。FIG. 2 is a graph showing the photocatalytic activity of a Pt—Au alloy photocatalyst according to the first aspect of the present invention.
【図３】図３は、本発明第二観点による〔Ｐｔ−Ａｕ〕
／ＴｉＯ2 合金・半導体複合光触媒の構造を示す概念図
である。FIG. 3 shows [Pt-Au] according to the second aspect of the present invention.
/ Is a conceptual diagram showing the structure of TiO 2 alloy, composite semiconductor photocatalyst.
【図４】図４は、本発明第二観点による〔Ｐｔ−Ａｕ〕
／ＴｉＯ2 合金・半導体複合光触媒の浄化能力を従来の
ＴｉＯ2 半導体光触媒と比較して示すグラフである。FIG. 4 shows [Pt-Au] according to the second aspect of the present invention.
/ Purification capacity of the TiO 2 alloy, composite semiconductor photocatalyst is a graph comparing the conventional TiO 2 semiconductor photocatalyst.
【図５】図５は、本発明第一および第二観点の各光触媒
の浄化能力を従来の光触媒と比較して示すグラフであ
る。FIG. 5 is a graph showing the purifying ability of each photocatalyst according to the first and second aspects of the present invention in comparison with a conventional photocatalyst.
Claims (4)
徴とする光触媒。1. A photocatalyst comprising gold particles supported on platinum.
更に半導体光触媒上に担持したことを特徴とする光触
媒。2. A photocatalyst comprising gold fine particles supported on platinum, and the platinum further supported on a semiconductor photocatalyst.
半導体光触媒が酸化チタン（ＴｉＯ2)、硫化カドミウム
（ＣｄＳ）、チタン酸ストロンチウム（ＳｒＴｉＯ3)、
チタン酸カリウム（Ｋ2 Ｔｉ6 Ｏ13）、酸化タンタル
（Ｔａ2 Ｏ5 ）から成る群から選択されることを特徴と
する光触媒。3. The photocatalyst according to claim 2, wherein said semiconductor photocatalyst is titanium oxide (TiO 2 ), cadmium sulfide (CdS), strontium titanate (SrTiO 3 ),
A photocatalyst selected from the group consisting of potassium titanate (K 2 Ti 6 O 13 ) and tantalum oxide (Ta 2 O 5 ).
載の光触媒と、該光触媒への光照射手段とを備えたこと
を特徴とする光触媒装置。4. A photocatalyst device comprising: the photocatalyst according to claim 1; and means for irradiating the photocatalyst with light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10063581A JPH11253818A (en) | 1998-03-13 | 1998-03-13 | Photocatalyst and photocatalytic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10063581A JPH11253818A (en) | 1998-03-13 | 1998-03-13 | Photocatalyst and photocatalytic device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11253818A true JPH11253818A (en) | 1999-09-21 |
Family
ID=13233385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10063581A Withdrawn JPH11253818A (en) | 1998-03-13 | 1998-03-13 | Photocatalyst and photocatalytic device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11253818A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001269541A (en) * | 2000-03-24 | 2001-10-02 | Ngk Insulators Ltd | Photocatalytic treatment device |
| WO2004112958A1 (en) * | 2003-06-19 | 2004-12-29 | Carrier Corporation | Air purification system comprising gold/titanium dioxide photocatalyst |
| JP2008104996A (en) * | 2006-10-27 | 2008-05-08 | Central Japan Railway Co | Photocatalyst, coating liquid for forming photocatalyst and method for manufacturing photocatalyst |
| JP2010005568A (en) * | 2008-06-27 | 2010-01-14 | Nbc Meshtec Inc | Composite catalyst carrier and its manufacturing method |
| US10618002B2 (en) | 2018-12-20 | 2020-04-14 | Tenneco Automotive Operating Company Inc. | System and method for treating ambient air |
-
1998
- 1998-03-13 JP JP10063581A patent/JPH11253818A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001269541A (en) * | 2000-03-24 | 2001-10-02 | Ngk Insulators Ltd | Photocatalytic treatment device |
| WO2004112958A1 (en) * | 2003-06-19 | 2004-12-29 | Carrier Corporation | Air purification system comprising gold/titanium dioxide photocatalyst |
| JP2008104996A (en) * | 2006-10-27 | 2008-05-08 | Central Japan Railway Co | Photocatalyst, coating liquid for forming photocatalyst and method for manufacturing photocatalyst |
| JP2010005568A (en) * | 2008-06-27 | 2010-01-14 | Nbc Meshtec Inc | Composite catalyst carrier and its manufacturing method |
| US10618002B2 (en) | 2018-12-20 | 2020-04-14 | Tenneco Automotive Operating Company Inc. | System and method for treating ambient air |
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