JPH0365231B2 - - Google Patents
Info
- Publication number
- JPH0365231B2 JPH0365231B2 JP60159524A JP15952485A JPH0365231B2 JP H0365231 B2 JPH0365231 B2 JP H0365231B2 JP 60159524 A JP60159524 A JP 60159524A JP 15952485 A JP15952485 A JP 15952485A JP H0365231 B2 JPH0365231 B2 JP H0365231B2
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor
- film
- solution
- membrane
- present
- 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
- 239000004065 semiconductor Substances 0.000 claims description 26
- 239000000084 colloidal system Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 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 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、多孔性膜に半導体コロイドを保持さ
せてなる光機能性膜に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a photofunctional film formed by holding a semiconductor colloid in a porous film.
半導体電極により水を光分解して水素と酸素を
得る方法が発表されて以来、半導体光触媒の開発
が盛んである。半導体光触媒の応用例としては、
バイオマスを光分解して水素を製造する技術が、
廃棄物の利用による水素製造法として注目されて
いる。またベンゼンからフエノールを合成する方
法やアミノ酸の合成等の有機合成への応用も今後
発展するものと思われる。また有機ハロゲン化合
物やキレート化合物などの公害物質の分解も半導
体触媒の重要な応用分野である。半導体の触媒作
用は半導体と溶液の界面で起るので、表面積が大
きい粉末を用いる方が、電極を用いるより、反応
効率が大きい。このため上記の応用分野ではもつ
ぱら粉末が用いられている。一方、粉末は溶液中
に懸濁して用いるので、反応後、濾過や遠心分離
により、反応物から半導体粉末を除かなければな
らないという欠点がある。このため反応を連続的
に行うことができず、このことが半導体触媒の実
用化の大きな妨げとなつている。
Semiconductor photocatalysts have been actively developed ever since a method for photolyzing water using semiconductor electrodes to obtain hydrogen and oxygen was announced. Examples of applications of semiconductor photocatalysts include:
The technology to produce hydrogen by photolyzing biomass is
This method is attracting attention as a hydrogen production method using waste materials. Applications to organic synthesis, such as methods for synthesizing phenol from benzene and amino acid synthesis, are also expected to develop in the future. Decomposition of pollutants such as organic halogen compounds and chelate compounds is also an important application field for semiconductor catalysts. Since the catalytic action of a semiconductor occurs at the interface between the semiconductor and the solution, using a powder with a large surface area has a higher reaction efficiency than using an electrode. For this reason, Motpara powder is used in the above application fields. On the other hand, since the powder is used suspended in a solution, there is a drawback that the semiconductor powder must be removed from the reactant by filtration or centrifugation after the reaction. For this reason, the reaction cannot be carried out continuously, which is a major hindrance to the practical application of semiconductor catalysts.
本発明は、従来技術に見られる前記欠点を克服
した、半導体粉末の特徴を生かし、かつ流動式反
応装置に用いることの可能な半導体を含む光機能
膜を提供することを目的とする。
An object of the present invention is to provide an optical functional film containing a semiconductor that overcomes the above-mentioned drawbacks found in the prior art, takes advantage of the characteristics of semiconductor powder, and can be used in a fluidized reactor.
本発明によれば、多孔性膜に半導体コロイドを
保持させたことを特徴とする光機能性膜が提供さ
れる。
According to the present invention, there is provided a photofunctional film characterized in that a porous film holds a semiconductor colloid.
本発明の光機能性膜は、バイオマス、アルコー
ル等の存在下で水を光分解して、水素を製造する
ことができる。また環境汚染上の問題となつてい
るトリクロルエチレン、テトラクロルエチレン、
ジクロルメタンの有機ハロゲン化合物の除去に用
いることできる。更に有機合成において、ベンゼ
ンの酸化によるフエノールの製造や不飽和脂肪酸
の水素化に光触媒として用いることができる。本
発明の光機能性膜を流動式の反応槽と組み合せて
用いることにより、上記のような反応を連続的に
行なわせることできる。 The photofunctional film of the present invention can produce hydrogen by photolyzing water in the presence of biomass, alcohol, and the like. In addition, trichlorethylene, tetrachlorethylene, which has become an environmental pollution problem,
It can be used to remove organic halogen compounds from dichloromethane. Furthermore, in organic synthesis, it can be used as a photocatalyst in the production of phenol through the oxidation of benzene and in the hydrogenation of unsaturated fatty acids. By using the photofunctional film of the present invention in combination with a fluidized reaction tank, the above reactions can be carried out continuously.
本発明に用いる多孔性膜は、孔のサイズが0.01
〜10μmの範囲にあるものが適しているが、これ
に限定されるものではない。このような多孔性膜
としては、従来公知のもの、例えば、市販のメン
ブランフイルターやガラスフイルター等が用いら
れる。 The porous membrane used in the present invention has a pore size of 0.01
Those in the range of ~10 μm are suitable, but are not limited thereto. As such a porous membrane, conventionally known ones such as commercially available membrane filters and glass filters can be used.
本発明に用いる半導体は、微粒子コロイドにし
得るものであれば殆んど全てのものを用いること
ができ、その具体的半導体の種類は、その使用目
的に応じて適当に選択される。例えば、水分解の
目的には、二酸化チタン、チタン酸ストロンチウ
ム、硫化カドミウム等が好ましく用いられる。 As the semiconductor used in the present invention, almost any semiconductor can be used as long as it can be made into a fine colloid, and the specific type of semiconductor is appropriately selected depending on the purpose of use. For example, for the purpose of water splitting, titanium dioxide, strontium titanate, cadmium sulfide, etc. are preferably used.
本発明の光機能性膜は、多孔性膜の孔サイズに
近い粒子径の分布を持つ半導体コロイド溶液を、
多孔性膜で繰返し濾過し、半導体の微粒子コロイ
ドを多孔性膜に保持させることによつて製造され
る。この場合、半導体の微粒子コロイド溶液は、
一般には、半導体の合成法に基づいて調製するこ
とができる。即ち、半導体合成法に従つて、半導
体化合物のコロイド溶液を形成し、これを加熱熟
成し、粒子を成長させる。コロイド粒子の粒子径
のコントロールは、この熟成温度と熟成時間を調
節することにより行うことができる。この半導体
コロイド溶液の調製を、例えば、二酸化チタンの
場合について示すと、二酸化チタンの合成法に従
つて、先ず、蒸留水に四塩化チタンを微量ずつ添
加し、加水分解させることにより、二酸化チタン
のヒドロゾル微粒子のコロイド溶液を形成し、こ
れを熟成すればよい。 The photofunctional film of the present invention uses a semiconductor colloid solution with a particle size distribution close to the pore size of the porous film.
It is manufactured by repeatedly filtering through a porous membrane and retaining the semiconductor microparticle colloid in the porous membrane. In this case, the semiconductor fine particle colloidal solution is
Generally, it can be prepared based on a semiconductor synthesis method. That is, according to a semiconductor synthesis method, a colloidal solution of a semiconductor compound is formed, and this is heat-ripened to grow particles. The particle size of colloidal particles can be controlled by adjusting the aging temperature and aging time. To explain the preparation of this semiconductor colloidal solution in the case of titanium dioxide, for example, according to the titanium dioxide synthesis method, titanium tetrachloride is first added in small amounts to distilled water and hydrolyzed to form titanium dioxide. A colloidal solution of hydrosol fine particles may be formed and this may be aged.
本発明の光機能性膜は、前記のようにして得ら
れる半導体微粒子のみを保持させた膜のままでも
使用可能であるが、必要に応じ、その半導体の触
媒効果を向上させるために、さらに、金属を担持
させて用いることができる。この場合、担持させ
る金属としては、例えば、白金、パラジウム、ロ
ジウム、ルテニウム、イリジウム、銅等が挙げら
れ、水の分解を目的とする場合には、特に、白金
やパラジウムの使用が好ましい。膜に対してこれ
ら金属を担持させるためには、金属イオンの水溶
液に窒素やアルゴン等の不活性ガスを導入して溶
存酸素を除去した後に、この溶液に膜を浸して光
を照射する。この操作において、金属イオンが膜
面に沈漬しにくいときは、金属イオン溶液にアス
コルビン酸を加えることにより、金属の沈漬を効
率よく行わせることができる。また、膜に対する
金属の担持は、金属蒸着法等によつて行うことも
できる。 The photofunctional film of the present invention can be used as a film retaining only the semiconductor fine particles obtained as described above, but if necessary, in order to improve the catalytic effect of the semiconductor, It can be used by supporting a metal. In this case, examples of the supported metal include platinum, palladium, rhodium, ruthenium, iridium, copper, etc. When the purpose is to decompose water, it is particularly preferable to use platinum or palladium. In order to support these metals on the film, an inert gas such as nitrogen or argon is introduced into an aqueous solution of metal ions to remove dissolved oxygen, and then the film is immersed in this solution and irradiated with light. In this operation, if metal ions are difficult to sink into the membrane surface, the metal can be efficiently immersed by adding ascorbic acid to the metal ion solution. Further, metal can also be supported on the film by a metal vapor deposition method or the like.
本発明の光機能性膜は、その表面の補強を行う
ために、さらに、その表面を高分子被膜で被覆す
ることができる。この場合、被膜形成用高分子と
しては、ポリビニルアルコール、ゼラチン、ポリ
ビニルピロリドン、ポリアクリル酸、ポリ酢酸ビ
ニル、ポリウレタン等の水溶性ないしエマルジヨ
ン形成性のものが用いられ、光機能性膜の用途と
の関連で適当のものが選択される。例えば、水溶
液系に用いる場合には、親水性高分子が好ましく
使用される。これらの高分子は、１％程度の濃度
の溶液として適用され、その付着量（乾燥重量基
準）は、１〜５ｇ／m2、好ましくは２〜３ｇ／m2
程度である。 The surface of the optically functional film of the present invention can be further coated with a polymer film in order to reinforce the surface. In this case, the film-forming polymer used is a water-soluble or emulsion-forming polymer such as polyvinyl alcohol, gelatin, polyvinylpyrrolidone, polyacrylic acid, polyvinyl acetate, or polyurethane, which is suitable for use as a photofunctional film. An appropriate one is selected based on the relationship. For example, when used in an aqueous solution system, hydrophilic polymers are preferably used. These polymers are applied as a solution with a concentration of about 1%, and the amount of adhesion (based on dry weight) is 1 to 5 g/m 2 , preferably 2 to 3 g/m 2
That's about it.
本発明の光機能性膜は、前記したような各種の
光反応触媒として使用され、反応終了後、反応系
から分離することが容易であり、また流動式の反
応槽と組合せて用いることにより、連続的に反応
を行わせることができる。
The photofunctional membrane of the present invention can be used as a catalyst for various photoreactions as described above, and can be easily separated from the reaction system after the reaction is completed, and can be used in combination with a fluidized reaction tank. The reaction can be carried out continuously.
次に本発明を実施例によりさらに詳細に説明す
る。
Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
アイスバス中で冷却した蒸留水100mlを撹拌し
ながら、四塩化チタンの５mlを微量ずつ、ゆつく
り加えた、生ずる微細な二酸化チタンのコロイド
溶液の30c.c.を80℃で約10分間熟成した。このコロ
イド溶液をザルトリウス製メンブランフイルター
SM1160（濾紙径4.5cm、孔径0.2μm）で濾過した。
濾液を熟成して、再び濾過し、同様の操作を数回
繰り返してコロイドを膜中に保持させた。この膜
を流水で20分間水洗した後に、0.5％塩化白金酸
を含み、炭酸ナトリウムと塩酸でPH4.0に調節し
た水溶液に浸した。窒素ガスを20分間送つた後
に、窒素の送気を続けながら、500W超高圧水銀
灯で、片面30分ずつ、両面光照射した。表面に白
金が沈浸した膜を塩酸溶液に１分間浸漬した後
に、流水で十分に水洗した。このようにして、本
発明の光機能性膜を得た。Example 1 5 ml of titanium tetrachloride was slowly added in small portions to 100 ml of distilled water cooled in an ice bath with stirring, and 30 c.c. of the resulting fine colloidal solution of titanium dioxide was heated to about 10 ml at 80°C. Aged for minutes. Filter this colloid solution through a Sartorius membrane filter.
It was filtered using SM1160 (filter paper diameter: 4.5 cm, pore size: 0.2 μm).
The filtrate was aged and filtered again, and the same operation was repeated several times to retain the colloid in the membrane. After washing this membrane with running water for 20 minutes, it was immersed in an aqueous solution containing 0.5% chloroplatinic acid and adjusted to pH 4.0 with sodium carbonate and hydrochloric acid. After supplying nitrogen gas for 20 minutes, both sides were irradiated with light for 30 minutes on each side using a 500W ultra-high pressure mercury lamp while continuing to supply nitrogen gas. The membrane with platinum precipitated on its surface was immersed in a hydrochloric acid solution for 1 minute, and then thoroughly washed with running water. In this way, the optical functional film of the present invention was obtained.
実施例 ２
実施例１で調製した半導体固定膜をパイレツク
スガラス製サンプルビン（容積30ml）に入れ、エ
タノールと水の１：１溶液15mlを加え、シリコン
ゴムで栓をした。これを100W超高圧水銀灯で
310nmのカツトフイルターを通して５時間照射し
た。サンプルビンの中の気体の一部をガスクロマ
トグラフで分析した。この時11mlの水素が得られ
た。Example 2 The semiconductor fixed film prepared in Example 1 was placed in a Pyrex glass sample bottle (volume: 30 ml), 15 ml of a 1:1 solution of ethanol and water was added, and the bottle was stoppered with silicone rubber. This was done using a 100W ultra-high pressure mercury lamp.
It was irradiated for 5 hours through a 310 nm cut filter. A portion of the gas in the sample bottle was analyzed using a gas chromatograph. At this time, 11 ml of hydrogen was obtained.
実施例 ３
実施例１と同様にして、二酸化チタンコロイド
を保持し、白金を担持したザルトリウス製メンブ
ランフイルターSM11307（濾紙径4.5cm、孔径
0.01μm）を10-2モルEDTA（エチレンジアミン四
酢酸二ナトリウム）の水溶液15μに浸して、実
施例２と同様の方法で１時間光照射した。発生し
たガスを実施例２と同様の方法で分析した。これ
により0.8mlの水素が得られた。Example 3 In the same manner as in Example 1, Sartorius membrane filter SM11307 (filter paper diameter 4.5 cm, pore size
0.01 μm) was immersed in a 15 μm aqueous solution of 10 −2 mol EDTA (disodium ethylenediaminetetraacetate) and irradiated with light for 1 hour in the same manner as in Example 2. The generated gas was analyzed in the same manner as in Example 2. This yielded 0.8 ml of hydrogen.
実施例 ４
実施例１と同様にして調製した半導体固定膜の
片面に、１％ポリビニルアルコール（PVA）水
溶液の0.4mlを流し、一昼夜乾燥した。これを実
施例２と同様にして、PVA被覆面を１時間光照
射した。これにより0.85mlの水素が得られた。Example 4 0.4 ml of a 1% polyvinyl alcohol (PVA) aqueous solution was poured onto one side of a semiconductor-fixed membrane prepared in the same manner as in Example 1, and dried overnight. This was carried out in the same manner as in Example 2, and the PVA-coated surface was irradiated with light for 1 hour. This yielded 0.85 ml of hydrogen.
Claims (1)
を特徴とする光機能性膜。1. A photofunctional film characterized by having a porous film hold a semiconductor colloid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60159524A JPS6219245A (en) | 1985-07-19 | 1985-07-19 | Optically functional film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60159524A JPS6219245A (en) | 1985-07-19 | 1985-07-19 | Optically functional film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6219245A JPS6219245A (en) | 1987-01-28 |
| JPH0365231B2 true JPH0365231B2 (en) | 1991-10-11 |
Family
ID=15695648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60159524A Granted JPS6219245A (en) | 1985-07-19 | 1985-07-19 | Optically functional film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6219245A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63248443A (en) * | 1987-04-01 | 1988-10-14 | Agency Of Ind Science & Technol | Photooxidation catalyst and its production |
| JPH01135842A (en) * | 1987-11-21 | 1989-05-29 | Agency Of Ind Science & Technol | Photocatalyst-immobilized membrane |
| JP2006326530A (en) * | 2005-05-27 | 2006-12-07 | Hiroshima Univ | Nanoporous titanium oxide membrane and method for treating volatile organic compound using the same |
| WO2012058869A1 (en) * | 2010-11-04 | 2012-05-10 | 中国科学院理化技术研究所 | Semiconductor photocatalyst for the photocatalytic reforming of biomass derivatives for hydrogen generation, and preparation and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5820701A (en) * | 1981-07-23 | 1983-02-07 | Mitsubishi Electric Corp | Semiconductor element for hydrogen generation |
-
1985
- 1985-07-19 JP JP60159524A patent/JPS6219245A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5820701A (en) * | 1981-07-23 | 1983-02-07 | Mitsubishi Electric Corp | Semiconductor element for hydrogen generation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6219245A (en) | 1987-01-28 |
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