JP2002301369A - PHOTOCATALYST USING OXIDE CONTAINING TYPICAL METALLIC ION IN d10 ELECTRONIC STATE - Google Patents
PHOTOCATALYST USING OXIDE CONTAINING TYPICAL METALLIC ION IN d10 ELECTRONIC STATEInfo
- Publication number
- JP2002301369A JP2002301369A JP2001110870A JP2001110870A JP2002301369A JP 2002301369 A JP2002301369 A JP 2002301369A JP 2001110870 A JP2001110870 A JP 2001110870A JP 2001110870 A JP2001110870 A JP 2001110870A JP 2002301369 A JP2002301369 A JP 2002301369A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- water
- ruo
- alkaline earth
- electronic state
- 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 36
- 150000001455 metallic ions Chemical class 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 14
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 12
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006303 photolysis reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- -1 alkaline earth metal tin salt Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- MRZMQYCKIIJOSW-UHFFFAOYSA-N germanium zinc Chemical group [Zn].[Ge] MRZMQYCKIIJOSW-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な光触媒に関
する。特にＲｕＯ2担持Ｂ2ＸnＯm（ここでＢはアルカリ
土類金属原子またはＺｎであり、Ｘはｄ10電子状態の金
属イオンであり、ｎ＝（ｍ−１）/３であり、ｎは１ま
たは２である。）からなる光触媒、特に水の完全分解用
光触媒に関する。The present invention relates to a novel photocatalyst. Particularly RuO 2 supported B 2 X n O m (B here is an alkaline earth metal atom or Zn, X is a d 10 of electronic state metal ion, n = (m-1) / a 3, n Is 1 or 2.), especially a photocatalyst for complete decomposition of water.
【０００２】[0002]
【従来技術】水の光分解反応は光エネルギー変換の観点
から興味が持たれている。また、水の光分解反応に活性
を示す光触媒は、光吸収、電荷分離、表面での酸化還元
反応といった機能を備えた高度な光機能材料と見ること
ができる。工藤、加藤等は、タンタル酸アルカリ、アル
カリ土類等が、前記水の完全光分解反応に高い活性を示
す光触媒であることを多くの先行文献を挙げて説明して
いる〔例えば、Catal.Lett.,58(1999).153-155、Chem.L
ett.,(1999),1207、表面，Vol.36,No.12(1998),625-645
（文献Ａという）〕。2. Description of the Related Art The photolysis reaction of water is of interest from the viewpoint of light energy conversion. In addition, a photocatalyst that is active in the photodecomposition reaction of water can be regarded as an advanced photofunctional material having functions such as light absorption, charge separation, and redox reaction on the surface. Kudo, Kato et al. Have described many prior documents that alkali tantalate, alkaline earth, and the like are photocatalysts exhibiting high activity in the complete photolysis reaction of water (for example, Catal. Lett. ., 58 (1999) .153-155, Chem.L
ett., (1999), 1207, Surface, Vol. 36, No. 12 (1998), 625-645.
(Referred to as Document A)].
【０００３】前記文献Ａにおいては、水を光触媒を用い
て水素と酸素に分解する反応を進めるのに有用な光触媒
材料について解説しており、水の完全光分解反応用光触
媒についての多くの示唆をしている。先ず、水の完全光
分解において、タンタル酸塩は、助触媒なしに純水から
水素と酸素を量論比で生成する光触媒として機能するこ
とを見出したこと、また、ＮｉＯ助触媒を担持させるこ
とにより、前記触媒活性が飛躍的に向上することが分か
ったことが報告されている（６３５頁右欄）。また、Ｋ
4Ｎｂ6Ｏ17についても、純水から助触媒なしに水素と酸
素を生成させることができること、また、これを粉砕し
て微結晶にしたものは著しく高い活性を示すとの報告が
あることを解説している。更に、Ｋ2Ｌａ2Ｔｉ3Ｏ10の
様なペロブスカイト構造を有する化合物は、層間が水和
し易いことにより光触媒活性が高いことが説明されてい
る。[0003] Reference A describes a photocatalyst material useful for promoting the reaction of decomposing water into hydrogen and oxygen using a photocatalyst, and provides many suggestions for a photocatalyst for complete photolysis of water. are doing. First, in the complete photolysis of water, tantalate was found to function as a photocatalyst that generates hydrogen and oxygen at a stoichiometric ratio from pure water without a cocatalyst. Reported that the catalyst activity was dramatically improved (p. 635, right column). Also, K
For even 4 Nb 6 O 17, it is possible to produce hydrogen and oxygen without the co-catalyst from the pure water, also that there are reported to show a significantly higher activity obtained by this ground to fine crystals Explains. Further, it is described that a compound having a perovskite structure such as K 2 La 2 Ti 3 O 10 has high photocatalytic activity due to easy hydration between layers.
【０００４】また、６２９頁の図６には不均一系光触媒
材料の主要構成元素について解説し、ｄ0およびｄ10の
電子配置を有する遷移金属イオンまたはｐブロックの金
属イオンからなる酸化物であることが述べられている。
そして、６４０頁にはＩｎ2Ｏ3とＺｎＯ積層については
メタノールの分解による水素発生やＡｇＮＯ3分解によ
る酸素発生、およびβ−Ｇａ2Ｏ3についてはＩｎ2Ｏ3と
固溶体を形成させて用いることなどが解説されている。
ただし、Ｇｅ、Ｓｎ、Ｓｂについて何らの解説もされて
いない。FIG. 6 on page 629 describes the main constituent elements of the heterogeneous photocatalyst material, which is an oxide composed of a transition metal ion having a d 0 and d 10 electron configuration or a p-block metal ion. That is stated.
On page 640, for the In 2 O 3 and ZnO stacked layers, hydrogen is generated by decomposition of methanol and oxygen is generated by decomposition of AgNO 3 , and β-Ga 2 O 3 is used by forming a solid solution with In 2 O 3. Are explained.
However, Ge, Sn, and Sb are not described at all.
【０００５】特許出願２０００−２４５６９０におい
て、ＲｕＯ2担持Ａ2ＸnＯmまたはＲｕＯ2担持ＢＸnＯm
（ここでＡはアルカリ金属原子、Ｂはアルカリ土類金属
原子またはＺｎであり、Ｘはｄ10電子状態の金属イオン
であり、ｎ＝ｍ/２またはｎ＝ｍ/３であり、ｎは２であ
る。）からなる光触媒として、ＸはＩｎ、ＧａまたはＳ
ｂであり、アルカリ金属原子はＮａ、Ｋ又はＲｂ、アル
カリ土類金属原子はＣａ、Ｓｒ又はＢａである光触媒が
完全分解用光触媒として特許出願されている。しかし、
ＳｎとＧｅについては、光触媒となることは報告されて
いない。また、Ｓｂでは上記以外の組成については、光
触媒となることは報告されていない。[0005] In patent application 2000-245690, RuO 2 supported A 2 X n O m or RuO 2 supported BX n O m
(Where A is an alkali metal atom, B is an alkaline earth metal atom or Zn, X is a d 10 of electronic state metal ion, a n = m / 2 or n = m / 3, n is 2 X is In, Ga or S
b, the alkali metal atom is Na, K or Rb, and the alkaline earth metal atom is Ca, Sr or Ba. A patent application has been filed as a photocatalyst for complete decomposition. But,
Sn and Ge have not been reported to be photocatalysts. Further, it has not been reported that Sb has a composition other than the above as a photocatalyst.
【０００６】[0006]
【発明が解決しようとする課題】上記のような中で、本
発明者はｄ10の電子配置を有する遷移金属イオンを用い
た光触媒について高い活性を発現させるための研究検討
をし、特に水の光分解を可能にする触媒を提供すること
を課題として種々の化合物について多くの実験を繰り返
してきた。その中で、アルカリ土類金属とｄ10の電子配
置を有する典型金属Ｇｅ、Ｓｎ、または化学式（化学量
論）の異なるＳｂイオンとの塩が、ＲｕＯ2を担持させ
ることにより、前記先行技術のようにメタノールやＡｇ
ＮＯ3の分解ではなく、水の完全分解が可能であること
を発見し前記課題を解決した。In the above-described [0005] The present inventors have studies examined for the expression of high activity for photocatalytic using transition metal ions having electron configuration of d 10, in particular water Many experiments have been repeated on various compounds to provide a catalyst that enables photolysis. Among them, a typical metal Ge having electron configuration of an alkaline earth metal and d 10, Sn or Formula and salts with different Sb ions of (stoichiometric), by supporting a RuO 2, of the prior art Like methanol or Ag
The inventors have found that water can be completely decomposed instead of decomposing NO 3 , and the above problem has been solved.
【０００７】[0007]
【課題を解決するための手段】本発明は、ＲｕＯ2担持
Ｂ2ＸnＯm（ここでＢはアルカリ土類金属原子またはＺ
ｎであり、Ｘはｄ10電子状態の金属イオンであり、ｎ＝
（ｍ−１）/３であり、ｎは１または２である。）から
なる光触媒である。好ましくは、ＸはＧｅ、Ｓｎまたは
Ｓｂであり、アルカリ土類金属原子はＣａ、Ｓｒ又はＢ
ａであることを特徴とする前記光触媒であり、より好ま
しくは、前記光触媒がＲｕＯ2を担持した亜鉛ゲルマニ
ウム塩、アルカリ土類金属スズ塩、またはアルカリ土類
金属アンチモン塩であることを特徴とする水の光分解反
応用光触媒である。Means for Solving the Problems The present invention, RuO 2 supported B 2 X n O m (where B is an alkaline earth metal atom or Z
a n, X is a d 10 of electronic state metal ion, n =
(M-1) / 3, and n is 1 or 2. ). Preferably, X is Ge, Sn or Sb and the alkaline earth metal atom is Ca, Sr or B
a, wherein the photocatalyst is a zinc germanium salt supporting RuO 2 , an alkaline earth metal tin salt, or an alkaline earth metal antimony salt. It is a photocatalyst for the photolysis reaction of water.
【０００８】[0008]
【本発明の実施の態様】本発明をより詳細に説明する。
ここでは、ＲｕＯ2を担持したアルカリ土類スズ塩の調
製方法について述べるが、Ｇｅ塩、Ｓｂ塩おいても同様
の方法で合成することができる。 I．光触媒の作成方法 ａ．アルカリ土類金属スズ塩の調製は、アルカリ土類金
属の炭酸塩とスズ酸化物を所定のモル比で混合し、大気
下１０００℃で８時間焼成する。ＲｕＯ2担持触媒は、
Ｒｕのカルボニル錯体であるＲｕ3（ＣＯ）12、あるい
はＲｕ（ａｃａｃ）のＴＨＦ（テトラヒドロフラン）溶
液を用い、含浸法により、Ｒｕ金属の重量（ｗｔ）％が
０．２５〜２．０ｗｔ％となるように、前記のように調
製したスズ塩に担持させた後、２００〜４００℃で加熱
してＲｕＯ2とすることによって得られる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail.
Here, a method for preparing an alkaline earth tin salt supporting RuO 2 will be described, but a Ge salt and an Sb salt can be synthesized in the same manner. I. Method of making photocatalyst a. In preparing the alkaline earth metal tin salt, a carbonate of the alkaline earth metal and tin oxide are mixed at a predetermined molar ratio, and the mixture is fired at 1000 ° C. for 8 hours in the atmosphere. The RuO 2 supported catalyst is
Using a solution of Ru 3 (CO) 12 , which is a carbonyl complex of Ru, or a solution of Ru (acac) in THF (tetrahydrofuran), the weight (wt)% of Ru metal becomes 0.25 to 2.0 wt% by an impregnation method. As described above, after being supported on the tin salt prepared as described above, it is obtained by heating at 200 to 400 ° C. to obtain RuO 2 .
【０００９】II．光触媒の試験法 光触媒反応の活性の測定には、従来からこの技術分野で
使用されている、真空係、反応系および分析系から構成
される閉鎖循環系反応装置を用いた。該装置内で生成す
る気体は、反応循環装置に予め加えた１００Torrの圧力
のＡｒと共にピストンポンプにより反応中循環させ、反
応系に直結したガスクロマトグラフにより随時分析する
ことにより発生量が計測される。光触媒粉末、０．２５
ｇを、石英製の縦反応装置に入れ、蒸留水をさらにイオ
ン交換した純水に懸濁した。光触媒の撹拌には、反応循
環装置内に加えた１００Torrの圧力のＡｒのバブリング
によって行った。光照射には、５００ＷＸｅランプ光
〔波長域２６０ｎｍ〜６００ｎｍ〕あるいはＨｇ−Ｘｅ
ランプ光（波長域２４８ｎｍ〜 ４３６nm）を用いた。II. Test Method for Photocatalyst The activity of the photocatalytic reaction was measured using a closed-circulation system reactor conventionally used in this technical field and composed of a vacuum system, a reaction system, and an analysis system. The gas generated in the apparatus is circulated during the reaction by means of a piston pump together with Ar having a pressure of 100 Torr previously applied to the reaction circulation apparatus, and is analyzed as needed by a gas chromatograph directly connected to the reaction system to measure the amount of gas generated. Photocatalyst powder, 0.25
g was placed in a vertical reactor made of quartz, and distilled water was further suspended in ion-exchanged pure water. The stirring of the photocatalyst was performed by bubbling Ar at a pressure of 100 Torr applied in the reaction circulation device. For light irradiation, 500 WXe lamp light (wavelength range 260 nm to 600 nm) or Hg-Xe
Lamp light (wavelength range 248 nm to 436 nm) was used.
【００１０】[0010]
【実施例】実施例１ ＲｕＯ2担持Ｓｒ2ＳｎＯ4光触媒の活性 焼成温度を１０００℃にしてＳｒ2ＳｎＯ4を作製し、得
られた化合物をＸ線回折による解析を行った。主ピーク
は、２θ＝３０．６５゜、３１．２０゜、４４．７０゜
に生じ、ＪＳＰＤカード（２４−１２４１）に記載の回
折パターンとよい一致を示す回折パターンが得られた。Example 1 Activity of RuO 2 -supported Sr 2 SnO 4 photocatalyst Sr 2 SnO 4 was prepared at a firing temperature of 1000 ° C., and the obtained compound was analyzed by X-ray diffraction. Main peaks occurred at 2θ = 30.65 °, 31.20 °, and 44.70 °, and diffraction patterns showing good agreement with the diffraction pattern described in the JSPD card (24-1241) were obtained.
【００１１】Ｒｕ3（ＣＯ）12を担持させ４００℃で酸
化して、１重量％のＲｕＯ2を担持したＳｒ2ＳｎＯ4光
触媒を得、これを用いて前記IIに記載の閉鎖循環系反応
装置を用い、光触媒の活性と、その活性の経時変化を調
べた。光源としては、２００ＷＨｇ−Ｘｅランプを使用
した。その結果を図１に示す。なお、発生試験装置は閉
鎖系であるので、気相の水素および酸素を排気し、その
操作を３サイクル繰り返し、触媒の活性の変化を調べ
た。延べ時間で１０時間反応させた後も触媒活性は初期
の特性を維持していた。[0011] is oxidized with 400 ° C. by supporting Ru 3 (CO) 12, to give a 1 wt% of Sr 2 SnO 4 photocatalyst carrying RuO 2, closed circulation system reactor according to the II with this Was used to examine the activity of the photocatalyst and the change over time in the activity. As a light source, a 200 WHg-Xe lamp was used. The result is shown in FIG. Since the generation test device is a closed system, hydrogen and oxygen in the gas phase were exhausted, and the operation was repeated three cycles to examine the change in the activity of the catalyst. Even after the reaction was performed for a total of 10 hours, the catalyst activity maintained its initial properties.
【００１２】図２に、焼成温度を１０００℃で調製した
アルカリ土類金属、すなわち、カルシウム（ａ）、スト
ロンチウム（ｂ）、およびバリウム（ｃ）のスズ塩の拡
散反射ＵＶスペクトルを示す。３８０ｎｍ付近より光吸
収がはじまり、３００ｎｍでの緩やかな吸収と２７０ｎ
ｍより短波長での急な吸収構造をもち、２５０ｎｍで最
大吸収を示した。FIG. 2 shows diffuse reflection UV spectra of tin salts of alkaline earth metals, ie, calcium (a), strontium (b), and barium (c), prepared at a firing temperature of 1000 ° C. The light absorption starts from around 380 nm, and the gradual absorption at 300 nm and 270 n
It has a steep absorption structure at a wavelength shorter than m and shows maximum absorption at 250 nm.
【００１３】実施例２ ＲｕＯ2担持Ｚｎ2ＧｅＯ4の光触媒活性 １０００℃で焼成したＺｎ2ＧｅＯ 4 のＸ線回折パターン
において、主ピークは、２θ＝３０．７°、３３．２
°、３７．９°、４７．８°に現れた。最も高いピーク
は２θ＝３３．２°に生じた。この焼成温度で得られた
ものが、ＪＳＰＤカード（１１・０６８７）記載の回折
パターンとよく対応する回折パターンが得られた。図３
には、Ｒｕのカルボニル錯体Ｒｕ3（ＣＯ）12を用いて
浸含法により得られた、１重量％のＲｕＯ2を担持した
Ｚｎ2ＧｅＯ4光触媒の活性の経時変化を示す。水素と酸
素が生成し、延べ時間で３時間反応させた後も触媒活性
は初期の特性を維持した。[0013] In X-ray diffraction pattern of Example 2 RuO 2 supported Zn 2 GeO 4 of Zn 2 GeO 4 calcined at photocatalytic activity 1000 ° C., the main peak, 2θ = 30.7 °, 33.2
°, 37.9 ° and 47.8 °. The highest peak occurred at 2θ = 33.2 °. The diffraction pattern obtained at this firing temperature gave a diffraction pattern which corresponded well to the diffraction pattern described in the JSPD card (11-0687). FIG.
2 shows the time-dependent changes in the activity of a Zn 2 GeO 4 photocatalyst carrying 1% by weight of RuO 2 obtained by the impregnation method using a carbonyl complex of Ru 3 (CO) 12 . Hydrogen and oxygen were generated, and the catalyst activity maintained its initial properties even after reacting for a total of 3 hours.
【００１４】図４に、焼成温度を１０００℃で作成した
Ｚｎ2ＧｅＯ4のＵＶ拡散反射スペクトルを示す。３００
ｎｍ付近より光吸収がはじまり、２８０ｎｍでの緩やか
な吸収と２７０ｎｍより短波長での急な吸収構造をも
ち、２６０〜２３０ｎｍの範囲で最大吸収を示した。FIG. 4 shows the UV diffuse reflection spectrum of Zn 2 GeO 4 prepared at a firing temperature of 1000 ° C. 300
The light absorption starts at around nm, has a gradual absorption at 280 nm and a sharp absorption structure at a wavelength shorter than 270 nm, and has a maximum absorption in the range of 260 to 230 nm.
【００１５】実施例３ ＲｕＯ2担持アンチモン塩、Ｂ2Ｓｂ2Ｏ7（Ｂ＝Ｃａ、Ｓ
ｒ）の光触媒活性ＲｕＯ2担持Ｂ2Ｓｂ2Ｏ7（Ｂ＝Ｃａ、
Ｓｒ）の調製は、前記光活性触媒の調製方法にしたがっ
て実施した。ＲｕＯ2担持Ｂ2Ｓｂ2Ｏ7（Ｂ＝Ｃａ、Ｓ
ｒ）光触媒の水の光分解特性を図５に示す。（ａ）はＣ
ａ2Ｓｂ2Ｏ7であり、（ｂ）はＳｒ2Ｓｂ2Ｏ7である。Example 3 RuO 2 -supported antimony salt, B 2 Sb 2 O 7 (B = Ca, S
r) Photocatalytically active RuO 2 supported B 2 Sb 2 O 7 (B = Ca,
The preparation of Sr) was carried out according to the method for preparing a photoactive catalyst. RuO 2 supported B 2 Sb 2 O 7 (B = Ca, S
r) Photodegradation characteristics of water of the photocatalyst are shown in FIG. (A) is C
a 2 Sb 2 O 7 , and (b) Sr 2 Sb 2 O 7 .
【００１６】図６にＢ2Ｓｂ2Ｏ7（Ｂ＝Ｃａ、Ｓｒ）の
ＵＶ拡散反射スペクトルを示す。Ｃａ2Ｓｂ2Ｏ7（ａ）
において、光吸収は３８０ｎｍ付近から緩やかに始ま
り、３２０ｎｍで急激な吸収となり、２８０ｎｍでふた
たび緩やかな吸収となった。Ｓｒ3Ｓｂ2Ｏ7（ｂ）で
は、吸収端は３４０ｎｍで最大吸収は２８０ｎｍとなっ
た。この光触媒により水を水素と酸素に分解できること
が分かる。FIG. 6 shows a UV diffuse reflection spectrum of B 2 Sb 2 O 7 (B = Ca, Sr). Ca 2 Sb 2 O 7 (a)
In, the light absorption started gently at around 380 nm, became a sharp absorption at 320 nm, and became a gradual absorption again at 280 nm. With Sr 3 Sb 2 O 7 (b), the absorption edge was 340 nm and the maximum absorption was 280 nm. It can be seen that this photocatalyst can decompose water into hydrogen and oxygen.
【００１７】[0017]
【発明の効果】本発明は、水の完全分解反応を行う光触
媒が、従来ｄ0電子状態の金属塩のみに限られていたの
に対し、ｄ10電子状態の金属塩でも可能であることを発
見した点で、水の完全光分解用の新規な材料の開発に対
して貢献することは明らかである。According to the present invention, the photocatalyst to conduct the complete decomposition reaction of water, the contrast has been limited only to a metal salt of a conventional d 0 electronic states are possible in d 10 of electronic state metal salt It is clear that the findings contribute to the development of new materials for the complete photolysis of water.
【図１】 １重量％ＲｕＯ2担持Ｓｒ2ＳｎＯ4触媒の水
の完全分解特性FIG. 1 Complete water decomposition characteristics of 1 wt% RuO 2 supported Sr 2 SnO 4 catalyst
【図２】 Ｂ2ＳｎＯ4（Ｂ＝Ｃａ、Ｓｒ、Ｂａ）のＵＶ
拡散反射スペクトル特性FIG. 2 UV of B 2 SnO 4 (B = Ca, Sr, Ba)
Diffuse reflection spectrum characteristics
【図３】 １重量％ＲｕＯ2担持Ｚｎ2ＧｅＯ4光触媒の
水の光分解特性FIG. 3 Photodecomposition characteristics of water by 1 wt% RuO 2 -supported Zn 2 GeO 4 photocatalyst
【図４】 Ｚｎ2ＧｅＯ4のＵＶ拡散反射スペクトル特性[FIG. 4] UV diffuse reflection spectrum characteristics of Zn 2 GeO 4
【図５】 ＲｕＯ2担持Ｃａ2Ｓｂ2Ｏ7（ａ）、ＲｕＯ2
担持Ｓｒ2Ｓｂ2Ｏ7（ｂ）光触媒の水の光分解特性FIG. 5: RuO 2 -supported Ca 2 Sb 2 O 7 (a), RuO 2
Photodegradation characteristics of water on supported Sr 2 Sb 2 O 7 (b) photocatalyst
【図６】 Ｃａ2Ｓｂ2Ｏ7（ａ）およびＳｒ2Ｓｂ2Ｏ
7（ｂ）のＵＶ拡散反射スペクトル特性FIG. 6: Ca 2 Sb 2 O 7 (a) and Sr 2 Sb 2 O
7 (b) UV diffuse reflection spectrum characteristics
───────────────────────────────────────────────────── 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） Ｃ０１Ｇ 9/00 Ｃ０１Ｇ 17/00 17/00 19/00 Ａ 19/00 Ｂ０１Ｊ 23/64 １０１Ｍ Ｆターム(参考） 4G042 BA08 BB04 BC06 4G047 AA04 AB01 AC03 4G069 AA03 AA08 BA48A BB04A BB04B BB06A BB06B BC08A BC09A BC09B BC12A BC12B BC13A BC13B BC22A BC22B BC23A BC23B BC26A BC26B BC35A BC35B BC70A BC70B CC33 EC25 FA01 FB30 FC07──────────────────────────────────────────────────続 き Continued on the front page (51) Int. Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C01G 9/00 C01G 17/00 17/00 19/00 A 19/00 B01J 23/64 101M F-term (Reference) 4G042 BA08 BB04 BC06 4G047 AA04 AB01 AC03 4G069 AA03 AA08 BA48A BB04A BB04B BB06A BB06B BC08A BC09A BC09B BC12A BC12B BC13A BC13B BC22A BC22B BC23A BC23B BC26A BC26 BC30ABC BC35 BC35
Claims (4)
カリ土類金属原子またはＺｎであり、Ｘはｄ10電子状態
の金属イオンであり、ｎ＝（ｍ−１）/３であり、ｎは
１または２である。）からなる光触媒。1. A RuO 2 supported B 2 X n O m (B here is an alkaline earth metal atom or Zn, X is a d 10 of electronic state metal ion, n = (m-1) / 3 And n is 1 or 2.).
属原子またはＺｎであり、Ｘはｄ10電子状態の金属イオ
ンであり、ｎ＝（ｍ−１）/３であり、ｎは１または２
である。）が、１０００〜１２００℃で焼成した粉末焼
成法により得られたものであることを特徴とする請求項
１に記載の光触媒。2. B 2 X n O m (where B is an alkaline earth metal atom or Zn, X is a metal ion in the d 10 electronic state, n = (m−1) / 3, n is 1 or 2
It is. The photocatalyst according to claim 1, wherein the photocatalyst is obtained by a powder firing method fired at 1000 to 1200 ° C.
カリ土類金属原子はＣａ、Ｓｒ又はＢａであることを特
徴とする請求項１または２に記載の光触媒。3. The photocatalyst according to claim 1, wherein X is Ge, Sn or Sb, and the alkaline earth metal atom is Ca, Sr or Ba.
媒からなることを特徴とする水の完全分解用光触媒。4. A photocatalyst for completely decomposing water, comprising the photocatalyst according to any one of claims 1 to 3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004097924A (en) * | 2002-09-09 | 2004-04-02 | Japan Science & Technology Corp | PHOTOCATALYST USING COMPOSITE OXIDE CONTAINING MEAL ION IN d10 AND d0 ELECTRONIC STATE |
| JP2005246202A (en) * | 2004-03-03 | 2005-09-15 | Japan Science & Technology Agency | PHOTOCATALYST USING OXIDE CONTAINING p-BLOCK METAL ION IN d10-d10 ELECTRONIC STATE |
| US7015172B2 (en) * | 2001-07-12 | 2006-03-21 | Japan Science And Technology Agency | Phosphate photocatalyst comprising metal ion in d10 or d0 electron state |
| JP2008155099A (en) * | 2006-12-22 | 2008-07-10 | Nagaoka Univ Of Technology | Photocatalyst for decomposing water and organic matter, and manufacturing method of this photocatalyst |
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|---|---|---|---|---|
| JPH0788370A (en) * | 1993-09-24 | 1995-04-04 | Yasunobu Inoue | Photocatalyst and production of photocatalyst |
| JPH09271666A (en) * | 1996-04-04 | 1997-10-21 | Natl Inst For Res In Inorg Mater | Catalyst for purifying organochlorine compound in water |
| JP2002059008A (en) * | 2000-08-14 | 2002-02-26 | Japan Science & Technology Corp | Photocatalyst using oxide containing metal ions of d10 electron state |
-
2001
- 2001-04-10 JP JP2001110870A patent/JP4025029B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0788370A (en) * | 1993-09-24 | 1995-04-04 | Yasunobu Inoue | Photocatalyst and production of photocatalyst |
| JPH09271666A (en) * | 1996-04-04 | 1997-10-21 | Natl Inst For Res In Inorg Mater | Catalyst for purifying organochlorine compound in water |
| JP2002059008A (en) * | 2000-08-14 | 2002-02-26 | Japan Science & Technology Corp | Photocatalyst using oxide containing metal ions of d10 electron state |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7015172B2 (en) * | 2001-07-12 | 2006-03-21 | Japan Science And Technology Agency | Phosphate photocatalyst comprising metal ion in d10 or d0 electron state |
| JP2004097924A (en) * | 2002-09-09 | 2004-04-02 | Japan Science & Technology Corp | PHOTOCATALYST USING COMPOSITE OXIDE CONTAINING MEAL ION IN d10 AND d0 ELECTRONIC STATE |
| JP2005246202A (en) * | 2004-03-03 | 2005-09-15 | Japan Science & Technology Agency | PHOTOCATALYST USING OXIDE CONTAINING p-BLOCK METAL ION IN d10-d10 ELECTRONIC STATE |
| JP4567992B2 (en) * | 2004-03-03 | 2010-10-27 | 独立行政法人科学技術振興機構 | Photocatalyst using oxide containing p-block metal ion in d10-d10 electronic state |
| JP2008155099A (en) * | 2006-12-22 | 2008-07-10 | Nagaoka Univ Of Technology | Photocatalyst for decomposing water and organic matter, and manufacturing method of this photocatalyst |
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