JPH0339737B2 - - Google Patents
Info
- Publication number
- JPH0339737B2 JPH0339737B2 JP56098503A JP9850381A JPH0339737B2 JP H0339737 B2 JPH0339737 B2 JP H0339737B2 JP 56098503 A JP56098503 A JP 56098503A JP 9850381 A JP9850381 A JP 9850381A JP H0339737 B2 JPH0339737 B2 JP H0339737B2
- Authority
- JP
- Japan
- Prior art keywords
- tio
- catalyst
- dispersion
- ruo
- water
- 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.)
- Expired - Lifetime
Links
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000010955 niobium Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 12
- BZSVVCFHMVMYCR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical group [Ru].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 BZSVVCFHMVMYCR-UHFFFAOYSA-N 0.000 description 10
- 239000002002 slurry Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000000184 acid digestion Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SIDCPPUYOKZTEY-UHFFFAOYSA-K 2-pyridin-2-ylpyridine;ruthenium(3+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 SIDCPPUYOKZTEY-UHFFFAOYSA-K 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SEQHERDIZNZVAM-UHFFFAOYSA-N CN1C(C=CC=C1)=C1N(C=CC=C1)C Chemical compound CN1C(C=CC=C1)=C1N(C=CC=C1)C SEQHERDIZNZVAM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、水を光分解させるための新規な触媒
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel catalyst for the photolysis of water.
太陽エネルギーの作用による水の分解について
は既に知られている。而して、この分解は、可視
光線の照射により水溶液中にH2とO2を生ぜしめ
るべく適当な触媒上で反応することのできるレド
ツクス系の賦活錯体を形成させることを基礎とし
たものである。 The splitting of water by the action of solar energy is already known. This decomposition is therefore based on the formation of a redox-based activating complex that can react on a suitable catalyst to produce H 2 and O 2 in an aqueous solution upon irradiation with visible light. be.
かくして、例えば、ZnO、TiO2およびWO2の
存在下キノンとFe3+により水を光分解させるこ
とが知られている。 Thus, for example, it is known to photolyze water with quinone and Fe 3+ in the presence of ZnO, TiO 2 and WO 2 .
水の光化学的分解に用いられる別の反応は、
PtおよびRuO2のコロイド触媒の存在での、ルテ
ニウムトリスビピリジルとメチルビオロゲン
（Ｎ，N′−ジメチルビピリジン）とからなるレド
ツクス系の使用を予見する。 Another reaction used for photochemical decomposition of water is
We foresee the use of a redox system consisting of ruthenium trisbipyridyl and methyl viologen (N,N'-dimethylbipyridine) in the presence of colloidal catalysts of Pt and RuO 2 .
更に特定するに、この系は下記態様で作動す
る。すなわち、ルテニウムトリスビピリジルはそ
の還元形Ru（bipi）2+において、可視光線の作用下
メチルビオロゲンMV2+を還元し、それによつ
て、
（最初） 還元化MV+を得る。これは、触媒Pt
上で水をH2に還元させ、而してMV2+の再生に
帰す；
（第二に） 酸化Ru（bipi）3 3+を得る。これは、
触媒RuO2上で水をO2に酸化させ、而してRu
（bipi）3 2+の再生に帰す。 More specifically, this system operates in the following manner. Thus, ruthenium trisbipyridyl, in its reduced form Ru(bipi) 2+ , reduces methyl viologen MV 2+ under the action of visible light, thereby obtaining (initially) reduced MV + . This is the catalyst Pt
Above, the water is reduced to H 2 , thus resulting in the regeneration of MV 2+ ; (Secondly) oxidized Ru(bipi) 3 3+ is obtained. this is,
Oxidize water to O 2 over a catalyst RuO 2 and then Ru
(bipi) Attributable to 3 2+ regeneration.
しかしながら、この方法により取得されるH2
およびO2の収率は非常に低い。 However, the H2 obtained by this method
and the yield of O2 is very low.
また、EDTA（エチルジアミノ四酢酸）とコロ
イド状白金の触媒の存在でルテニウムトリスビピ
リジル−メチルビオロゲンレドツクス系を用いる
ことが知られている。 It is also known to use a ruthenium trisbipyridyl-methylviologen redox system in the presence of a catalyst of EDTA (ethyldiaminotetraacetic acid) and colloidal platinum.
EDTAは、酸化形のルテニウムトリスビピリ
ジルにより酸化せしめられ、それ故H2のみが形
成される。而して、その収率は、上に例示した系
のそれよりは相当高いが、しかし依然としてかな
り低い。 EDTA is oxidized by the oxidized form of ruthenium trisbipyridyl and therefore only H 2 is formed. The yield is thus considerably higher than that of the systems exemplified above, but still quite low.
かくして、本発明の一つの目的は、高い分解率
を確保する新規な、水の光分解用触媒を提供する
ことである。 Thus, one object of the present invention is to provide a novel catalyst for the photolysis of water that ensures a high decomposition rate.
本発明の別の目的は、簡素化されたレドツクス
系により或はレドツクス系の不在で水の光分解を
遂行せしめうる新規な触媒を提供することであ
る。 Another object of the present invention is to provide a new catalyst that allows the photolysis of water to be carried out with a simplified redox system or in the absence of a redox system.
如上の目的はいずれも、本発明に依る水の光分
解用触媒にして、TiO2にニオブ（Nb）とルテニ
ウム（Ru）を含ませてなる触媒により達成され
る。 All of the above objectives are achieved by the catalyst for photolysis of water according to the present invention, which comprises TiO 2 containing niobium (Nb) and ruthenium (Ru).
ニオブはTiO2粒子内に在つて、ドーピング物
質として作用し、またルテニウムはRuO2の形で
TiO2の粒子表面に存在する。 Niobium is present in the TiO2 particles and acts as a doping material, and ruthenium is present in the form of RuO2 .
Exists on the surface of TiO 2 particles.
かくして、本発明の目的である触媒は、Nbで
ドーピング処理したTiO2の粒子にして、その表
面にRuO2を有するものよりなることを特徴とす
る。 Thus, the catalyst that is the object of the present invention is characterized by being composed of TiO 2 particles doped with Nb and having RuO 2 on the surface thereof.
触媒に含まれる酸化ルテニウムの量は、これを
TiO2に対するRuO2として算定するとき通常0.001
〜10重量％範囲、好ましくは0.02〜２重量％範囲
である。 The amount of ruthenium oxide contained in the catalyst is
Usually 0.001 when calculated as RuO 2 against TiO 2
-10% by weight, preferably 0.02-2% by weight.
また、触媒に含まれるニオブの量は、同じくこ
れをTiO2に対するNb2O5として算定するとき通
常0.001〜10重量％範囲、好ましくは0.1〜３重量
％範囲である。 Further, the amount of niobium contained in the catalyst is generally in the range of 0.001 to 10% by weight, preferably in the range of 0.1 to 3% by weight, when calculated as Nb 2 O 5 to TiO 2 .
TiO2はTiO2若しくはメタチタン酸（二酸化チ
タン水和物）としての非晶質ないし無定形で使用
され得、或は結晶形（ルチルないしアナターゼ）
で使用されうる。こ２種の結晶形は同時に存在し
うる。TiO2はまた、部分的に無定形且つ部分的
に結晶形の生成物よりなりうる。 TiO 2 can be used in amorphous form as TiO 2 or metatitanic acid (titanium dioxide hydrate) or in crystalline form (rutile or anatase).
can be used in These two crystal forms can exist simultaneously. TiO 2 may also consist of a partially amorphous and partially crystalline product.
TiO2粒子は50Å〜10ミクロン範囲、好ましく
は50Å〜10000Å範囲の粒度を有しうる。 The TiO2 particles may have a particle size in the range of 50 Å to 10 microns, preferably in the range of 50 Å to 10000 Å.
上記粒度は、凝集形状又は単一粒子形状で分散
体をなす粒子にかかわる。 The above particle sizes relate to particles forming a dispersion in agglomerated or single particle form.
本発明に従つた触媒は下記態様で調製されう
る。すなわち、
TiOSO4とFeSO4との溶液（イルメナイト又は
他のチタン含有物質を硫酸蒸解して得られる）
に、可溶ニオブ（五価）化合物例えばNb2O5を所
望の量で添加する。引続き、該溶液を90℃〜沸点
（好ましくは96〜108℃）範囲の温度にまで加熱
し、次いで水を希釈するが、その間、完全な加水
分解が達成されるまで上記温度を一定に保持す
る。これはブルメンフエルド（Blumenfeld）法
に依る。次いで、Nbを含有するメタチタン酸ス
ラリーを過し、洗浄する。 The catalyst according to the invention can be prepared in the following manner. i.e. a solution of TiOSO 4 and FeSO 4 (obtained by sulfuric acid digestion of ilmenite or other titanium-containing materials)
A soluble niobium (pentavalent) compound such as Nb 2 O 5 is added in the desired amount. Subsequently, the solution is heated to a temperature in the range from 90° C. to the boiling point (preferably 96-108° C.) and then diluted with water, while holding the temperature constant until complete hydrolysis is achieved. . This depends on the Blumenfeld method. Next, the Nb-containing metatitanic acid slurry is filtered and washed.
次いで、塊に、可溶ルテニウム塩例えば
RuCl3の溶液を所望の量で添加する。 The mass is then treated with a soluble ruthenium salt, e.g.
Add a solution of RuCl 3 in the desired amount.
かくして得られた生成物を引続き減圧例えば
300mmHg下、例えば110℃の温度で乾燥する。次
いで、好ましくは、生成物を大気中、例えば80〜
120℃で加熱する。 The product thus obtained is subsequently subjected to reduced pressure, e.g.
Dry under 300 mmHg, for example at a temperature of 110°C. The product is then preferably exposed to air, e.g.
Heat at 120℃.
この製造方法により、微晶質相がアナターゼで
ある部分的に無定形の生成物が得られる。 This production method gives a partially amorphous product whose microcrystalline phase is anatase.
別の製造方法は、例えば、Nb含有メタチタン
酸を、加熱下水酸化ナトリウムによる処理でチタ
ン酸ナトリウムに変換させ、次いでこのチタン酸
ナトリウムを、加熱下塩酸の添加により加水分解
してTiO2にすることである。 Another method of production is, for example, converting Nb-containing metatitanic acid to sodium titanate by treatment with sodium hydroxide under heating, and then hydrolyzing this sodium titanate to TiO 2 by adding hydrochloric acid under heating. It is.
かくして取得せる生成物を先の場合の如く
RuO2で被覆する。この場合、ルチル構造の、部
分水和した結晶質生成物が得られる。 The product thus obtained is as in the previous case
Coat with RuO2 . In this case, partially hydrated crystalline products of rutile structure are obtained.
本発明に従つた触媒は、コロイド状白金よりな
る水還元性触媒の存在で使用することができる。
レドツクス系は、例えば、ルテニウムトリスビピ
リジルとメチルビオロゲンとからなりうる。この
系において、式：TiO2／Nb／RuO2で表わすこ
とのできる本発明に従つた触媒の濃度は、例えば
100mg／〜１ｇ／範囲であり、またコロイド
状Ptは、例えば約30Åの径および約40mg／の
濃度を有する。 The catalyst according to the invention can be used in the presence of a water-reducing catalyst consisting of colloidal platinum.
The redox system may consist, for example, of ruthenium trisbipyridyl and methyl viologen. In this system, the concentration of the catalyst according to the invention, which can be expressed by the formula: TiO 2 /Nb/RuO 2 , is e.g.
100 mg/-1 g/, and the colloidal Pt has, for example, a diameter of about 30 Å and a concentration of about 40 mg/.
ルテニウムトリスビピリジルは例えば１〜３×
10-4モル／範囲の濃度を有し、メチルビオロゲ
ンは例えば約５×10-3モル／の濃度を有する。 Ruthenium trisbipyridyl is, for example, 1 to 3
It has a concentration in the range of 10 -4 mol/, methyl viologen for example has a concentration of about 5 x 10 -3 mol/.
この系と後述の系で、分散体のPHは３〜７範
囲、好ましくは3.8〜５範囲である。 In this system and the system described below, the pH of the dispersion is in the range of 3 to 7, preferably in the range of 3.8 to 5.
この系によるH2の収率は、触媒TiO2／Nb／
RuO2の代りにRuO2を用いて得たものより非常に
高く、しかも時を経ても安定なまゝである。 The yield of H 2 by this system is as follows: catalyst TiO 2 /Nb/
It is much higher than that obtained using RuO 2 instead of RuO 2 and also remains stable over time.
本発明に従つた触媒は、コロイド状Pt、ルテ
ニウムトリスビピリジル、メチルビオロゲンおよ
びEDTAを含有する系でも使用することができ
る。 The catalyst according to the invention can also be used in systems containing colloidal Pt, ruthenium trisbipyridyl, methyl viologen and EDTA.
この系でのEDTA濃度は、例えば５×10-2モ
ル／に等しく、また他成分の濃度は先に定義し
たものに等しい。この系によつて、H2のみが発
生し、しかもその収率は先の系で達成されるより
更に良好である。 The EDTA concentration in this system is, for example, equal to 5×10 -2 mol/and the concentrations of other components are equal to those defined above. With this system, only H 2 is generated, and the yield is even better than that achieved with the previous system.
本発明に従つた触媒は、簡素化されたレドツク
ス系と共に用いることができる。 The catalyst according to the invention can be used with simplified redox systems.
事実、TiO2／Nb／RuO2、ルテニウムトリス
ビピリジルおよびコロイド状白金よりなる系（す
なわち、メチルビオロゲンのない系）はH2とO2
を生成しうるとわかつた。 In fact, the system consisting of TiO 2 /Nb/RuO 2 , ruthenium trisbipyridyl and colloidal platinum (i.e. the system without methyl viologen ) is
It turns out that it is possible to generate
本発明による触媒は、レドツクス系の不在でも
使用することができる。事実、TiO2／Nb／
RuO2とコロイド状白金とよりなる系（すなわち、
ルテニウムトリスビピリジルおよびメチルビオロ
ゲンのない系）は、もし日光に代えて紫外線を照
射に用いるなら、H2とO2を生成しうるとわかつ
た。 The catalyst according to the invention can also be used in the absence of a redox system. In fact, TiO 2 /Nb/
A system consisting of RuO 2 and colloidal platinum (i.e.
Ruthenium trisbipyridyl and methyl viologen-free systems were found to be capable of producing H 2 and O 2 if ultraviolet light was used for irradiation instead of sunlight.
TiO2の粒子表面に存在するRuO2は連続的な被
覆を構成せず、恐らくは粒子表面を部分的にのみ
覆うRuO2斑点（座）があると思われる。 The RuO 2 present on the TiO 2 particle surface does not form a continuous coating, and there are probably RuO 2 spots that only partially cover the particle surface.
また、先に記述せる水の光分解系において、コ
ロイド状白金粒子はTiO2／Nb／RuO2触媒の表
面に吸着されていると思われる。 Furthermore, in the water photolysis system described above, colloidal platinum particles are thought to be adsorbed on the surface of the TiO 2 /Nb/RuO 2 catalyst.
本発明を更に例示するために、下記例を示す。 The following examples are provided to further illustrate the invention.
例 １ 本発明に従つた触媒を下記態様で調製した。Example 1 A catalyst according to the invention was prepared in the following manner.
イルメナイトを硫酸蒸解して得られるTiOSO4
とFe++の硫酸溶液にして、同イルメナイト鉱物
を給源とするニオブ（Nb）を0.2重量％（TiO2に
対するNb2O5として算定）量で含有する溶液を出
発物質とした。 TiOSO 4 obtained by sulfuric acid digestion of ilmenite
A solution containing niobium (Nb) sourced from the same ilmenite mineral in an amount of 0.2% by weight (calculated as Nb 2 O 5 relative to TiO 2 ) was used as the starting material.
而して、この溶液を95〜100℃にまで加熱し、
次いで水を用いて、硫酸溶液80容量部対水20容量
部の比に希釈した。これはブルメンフエルド法に
従つたものである。 Then, heat this solution to 95-100℃,
It was then diluted with water to a ratio of 80 parts by volume of sulfuric acid solution to 20 parts by volume of water. This follows the Blumenfeld method.
加水分解の終了時、50重量％のNaOH溶液200
mlに撹拌下90℃の温度で、メタチタン酸100ｇ
（TiO2に換算）を250ｇ（TiO2）／濃度の水性
スラリーとして加えた。 At the end of hydrolysis, 50% by weight NaOH solution 200
100 g of metatitanic acid at a temperature of 90 °C under stirring in ml
(calculated as TiO 2 ) was added as an aqueous slurry at a concentration of 250 g (TiO 2 )/concentration.
これを90℃の温度で２時間撹拌下に保ち、次
いで蒸留水により１：１容量比で希釈後過し、
洗液のNaO2含量が＜１ｇ／になるまで洗浄し
た。 This was kept under stirring for 2 hours at a temperature of 90°C, then diluted with distilled water in a 1:1 volume ratio and filtered.
Washing was carried out until the NaO 2 content of the washing liquid was <1 g/g/.
このようにして取得せるチタン酸ナトリウムを
200ｇ（TiO2）／濃度で水に分解させたもの
に、30重量％のHCl溶液を、撹拌下60℃までの加
熱後そのPHが３±0.1になる如き量で添加した。 Sodium titanate obtained in this way
To the solution dissolved in water at a concentration of 200 g (TiO 2 ), a 30% by weight HCl solution was added in an amount such that after heating to 60° C. with stirring, the pH was 3±0.1.
かくして得たスラリーに、30重量％濃度のHCl
を更に加えた。而して、その量は、HCl：TiO2
モル比が0.9になるようにした。次いで、該スラ
リーを沸点で２時間加熱した。 To the slurry thus obtained, HCl at a concentration of 30% by weight was added.
further added. Therefore, the amount is HCl: TiO2
The molar ratio was set to 0.9. The slurry was then heated at boiling point for 2 hours.
反応が終了したとき、TiO2濃度が100ｇ／に
なるまでスラリーを蒸留水で希釈した。かくして
得た分散体はルチル構造の針状TiO2粒子を含み、
また該粒子は1000〜2000Å範囲の粒度を有した。 When the reaction was finished, the slurry was diluted with distilled water until the TiO 2 concentration was 100 g/min. The dispersion thus obtained contains acicular TiO2 particles with a rutile structure,
The particles also had a particle size in the 1000-2000 Å range.
次いで、TiO21ｇを含有するスラリーにRuCl3
溶液（0.2ｇRuCl3・H2O／100mlH2O）１mlを加
えた。 RuCl 3 was then added to the slurry containing 1 g of TiO 2
1 ml of solution (0.2 g RuCl 3 .H 2 O/100 ml H 2 O) was added.
こRuCl3量は、TiO2に関して0.1％のRuO2を生
ずる如きものであつた。かくして得た分散体を次
いで超音波浴で約１分間均質化したのち、約300
mmHgの減圧下50℃で一液乾燥した。 This amount of RuCl 3 was such as to yield 0.1% RuO 2 with respect to TiO 2 . The dispersion thus obtained was then homogenized in an ultrasonic bath for about 1 minute, and then
One solution was dried at 50°C under a reduced pressure of mmHg.
日光の作用による水分解に触媒を用いることに
ついて以下説示する。 The use of catalysts for water splitting by the action of sunlight will be explained below.
触媒の水性分散体に微粉砕せるPt（粒径約30
Å）の水性分散体を混合した。かくして得た分散
体に次いで、一定の撹拌下、ルテニウムトリスビ
ピリジル塩化物とメチルビオロゲンを添加した。 Finely ground Pt (particle size approx. 30
Å) was mixed with an aqueous dispersion. Ruthenium trisbipyridyl chloride and methyl viologen were then added to the dispersion thus obtained under constant stirring.
PHを4.7の値に調整した。得られた分散体中下
記成分は次の如き濃度とわかつた：
Pt＝40mg／
TiO2／Nb／RuO2＝500mg／
ルテニウムトリスビピリジル塩化物
＝１×10-4モル／
メチルビオロゲン＝５×10-3モル／。 The pH was adjusted to a value of 4.7. The following components in the obtained dispersion were found to have the following concentrations: Pt = 40 mg / TiO 2 /Nb / RuO 2 = 500 mg / Ruthenium trisbipyridyl chloride = 1 × 10 -4 mol / Methyl viologen = 5 × 10 -3 mol/.
撹拌機を備えた、光学上平坦な窓二つをもつ35
mlガラスフラスコに分散体25mlを入れた。分散体
を窒素流れで処理して空気を排除した。試料に可
視光線を当てるために、450ワツトのキセノンラ
ンプを用いた。水を充たした15cm厚のガラスフラ
スコと400mm未満波長の放射線を保留するフイル
ターによつて、ランプより出た放射線から赤外成
分と紫外成分を取り除いた。 35 with two optically flat windows with a stirrer
25 ml of the dispersion was placed in a ml glass flask. The dispersion was treated with a stream of nitrogen to exclude air. A 450 Watt xenon lamp was used to illuminate the sample with visible light. Infrared and ultraviolet components were removed from the radiation emitted by the lamp using a 15 cm thick glass flask filled with water and a filter that retained radiation with wavelengths less than 400 mm.
照射の間、分散体を撹拌下に保持した。次い
で、フラスコ内に存在するガスを分析してH2と
O2の各濃度を求めた。その結果、溶液１当り
の水素発生速度が45ml／hr、酸素発生速度が16
ml／hrであるとわかつた。 The dispersion was kept under stirring during the irradiation. The gas present in the flask is then analyzed to determine H2 and
Each concentration of O 2 was determined. As a result, the hydrogen generation rate per solution was 45ml/hr, and the oxygen generation rate was 16ml/hr.
It was found to be ml/hr.
例 ２
本例は、EDTAを酸化させて水素のみを生成
する系に例１の触媒を使用することを例示する。Example 2 This example illustrates the use of the catalyst of Example 1 in a system that oxidizes EDTA to produce only hydrogen.
この目的に用いた分散体は、EDTAを５×10-2
モル／濃度で存在させるほかは例１の分散体と
同じものとする。 The dispersion used for this purpose contained EDTA at 5×10 -2
The dispersion is the same as in Example 1 except that it is present in molar/concentration.
この分散体を、例１に記載の如く、可視光線に
よる照射に付した。 This dispersion was subjected to irradiation with visible light as described in Example 1.
溶液１当りの水素発生速度が300ml／hrであ
るとわかつた。 The hydrogen generation rate per solution was found to be 300 ml/hr.
例 ３ 本発明に従つた触媒を下記態様で調製した。Example 3 A catalyst according to the invention was prepared in the following manner.
TiOSO4とFe2+の硫酸溶液（イルメナイトの硫
酸蒸解によつて取得）に、TiO2に対するNb2O5
量が0.4重量％になる量で採取せるNb2O5加え、
次いで95〜100℃にまで加熱したのち、水を用い
て硫酸溶液80容量部対水20容量部の比に希釈し
た。これはブルメンフエルド法によるものであ
る。 A sulfuric acid solution of TiOSO 4 and Fe 2+ (obtained by sulfuric acid digestion of ilmenite) contains Nb 2 O 5 for TiO 2
Add Nb 2 O 5 , which can be collected in an amount of 0.4% by weight,
It was then heated to 95-100°C and diluted with water to a ratio of 80 parts by volume of sulfuric acid solution to 20 parts by volume of water. This is based on the Blumenfeld method.
かくして得たメタチタン酸スラリーを過し、
また可溶不純物を除去すべく洗浄した。 The metatitanic acid slurry thus obtained was filtered,
It was also washed to remove soluble impurities.
TiO21ｇを含有する濃厚スラリーに、最終生成
物中のTiO2に対するRuO2量が0.1％になるように
RuCl31mg（RuO2として計算）含有液を添加し
た。次いで、生成物を約300mmHgの減圧下約110
℃で一液乾燥した。 A concentrated slurry containing 1 g of TiO 2 was added such that the amount of RuO 2 to TiO 2 in the final product was 0.1%.
A solution containing 1 mg of RuCl 3 (calculated as RuO 2 ) was added. The product is then dried under a vacuum of about 300 mmHg for about 110 min.
One liquid was dried at ℃.
TiO2は部分的に無定形であり且つまた微晶質
アナターゼ構造をも示した。それは一次粒子の凝
集体よりなり、そして該凝集体の粒度は1000〜
2000Åに等しく、また一次粒子の径は50〜150Å
範囲であつた。 TiO2 was partially amorphous and also exhibited microcrystalline anatase structure. It consists of aggregates of primary particles, and the particle size of the aggregates is 1000~
equal to 2000 Å, and the diameter of the primary particle is 50 to 150 Å
It was within the range.
而して、該触媒とコロイド状Ptおよびルテニ
ウムトリスビピロジル塩化物（メチルビオロゲン
不在）との分散体を調製した。 Thus, a dispersion of the catalyst, colloidal Pt, and ruthenium trisbipyrodyl chloride (in the absence of methyl viologen) was prepared.
分散体中の各成分濃度は次の如くであつた： Pt＝40mg／ TiO2／Nb／RuO2＝500mg／ ルテニウムトリスビピリジル塩化物 ＝２×10-4モル／。 The concentrations of each component in the dispersion were as follows: Pt = 40 mg/TiO 2 /Nb/RuO 2 = 500 mg/Ruthenium trisbipyridyl chloride = 2 x 10 -4 mol/.
分散体のPHは4.5であつた。 The pH of the dispersion was 4.5.
次いで、分散体を、例１と同じ可視光線による
照射に付した。 The dispersion was then subjected to the same visible light irradiation as in Example 1.
メチルビオロゲンの不在でさえ、系はH2とO2
を生ぜしめるとわかつた。 Even in the absence of methyl viologen, the system produces H 2 and O 2
It was found that it causes
例 ４
例３に記載せる触媒とコロイド状Pt（ルテニウ
ムトリスビピリジルとメチルビオロゲンは不在）
との分散体を調製した。Example 4 Catalyst described in Example 3 and colloidal Pt (Ruthenium trisbipyridyl and methyl viologen are absent)
A dispersion was prepared.
この分散体の成分濃度は下記の如くであつた： Pt＝40mg／ TiO2／Nb／RuO2＝500mg／。 The component concentrations of this dispersion were as follows: Pt = 40 mg/TiO 2 /Nb/RuO 2 = 500 mg/.
分散体のPHは4.5であつた。 The pH of the dispersion was 4.5.
照射処理は、400mm未満波長の放射線を取り除
くフイルターを存在させなかつたほかは例１で用
いたと同じランプで行なつた。それ故、分散体は
紫外線にも暴露されることとなる。 The irradiation process was carried out with the same lamp as used in Example 1, except that there was no filter present to remove radiation with wavelengths less than 400 mm. Therefore, the dispersion will also be exposed to UV radiation.
系は、ルテニウムトリスビピリジルとメチルビ
オロゲンのレドツクスを含まないが、H2とO2を
生ぜしめるとわかつた。 The system was found to be free of ruthenium trisbipyridyl and methyl viologen redox, but to generate H 2 and O 2 .
Claims (1)
の粒子をNbでドーピング処理してなり、しかも
該粒子表面にRuO2を含有することを特徴とする
触媒。 ２ ニオブの量（Nb2O5に換算した量）がTiO2
に関して0.001〜10重量％範囲であり、RuO2の量
（RuO2に換算した量）が同じくTiO2に関して
0.001〜10重量％範囲であることを特徴とする特
許請求の範囲第１項記載の触媒。 ３ TiO2の粒度が50Å〜10ミクロン範囲である
ことを特徴とする特許請求の範囲第１項又は２項
記載の触媒。[Claims] 1. TiO 2 as a catalyst for photodecomposing water.
A catalyst characterized in that the particles are doped with Nb and contain RuO 2 on the surface of the particles. 2 The amount of niobium (amount converted to Nb 2 O 5 ) is TiO 2
The amount of RuO2 (converted to RuO2 ) is in the range of 0.001 to 10% by weight with respect to TiO2 .
Catalyst according to claim 1, characterized in that the content is in the range of 0.001 to 10% by weight. 3. Catalyst according to claim 1 or 2, characterized in that the particle size of the TiO 2 is in the range of 50 Å to 10 microns.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT23123/80A IT1131867B (en) | 1980-06-30 | 1980-06-30 | CATALYST FOR THE DECOMPOSITION OF WATER BY MEANS OF SOLAR ENERGY |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5745345A JPS5745345A (en) | 1982-03-15 |
| JPH0339737B2 true JPH0339737B2 (en) | 1991-06-14 |
Family
ID=11204033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56098503A Granted JPS5745345A (en) | 1980-06-30 | 1981-06-26 | Catalyst for optically decomposing water |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5745345A (en) |
| IT (1) | IT1131867B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06102148B2 (en) * | 1986-01-22 | 1994-12-14 | 株式会社日立製作所 | Method and apparatus for oxidizing or reducing dissolved substances |
| EP1083990B1 (en) * | 1998-05-06 | 2002-07-03 | Siemens Aktiengesellschaft | Oxidation catalyst and method for catalytic oxidation |
| JPWO2005044447A1 (en) * | 2003-11-06 | 2007-05-17 | 東亞合成株式会社 | Composite oxidation type titania photocatalyst and use thereof |
-
1980
- 1980-06-30 IT IT23123/80A patent/IT1131867B/en active
-
1981
- 1981-06-26 JP JP56098503A patent/JPS5745345A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT1131867B (en) | 1986-06-25 |
| IT8023123A0 (en) | 1980-06-30 |
| JPS5745345A (en) | 1982-03-15 |
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