Fixation photocatalyst

[Detailed Description of the Invention]

[Industrial Application] The present invention relates to the fixed photocatalyst used in favor of oxidization decomposition and hydrogen generating of a fixed photocatalyst and the water which contains an organic matter or cyanogen especially.

[Description of the Prior Art] In recent years, it was found out that it becomes possible to produce disassembly of water and hydrogen generation using an oxidation-reduction reaction. (For example, ceramics Volume [ 2nd ] No. 4 (April, Showa 61), the 326 - 333rd page). an electron arises in a conducting zone, and an electron hole produces in a valence band, and this is Richness at this energy, when the semiconductor particles of TlO2 grade are excited with the light of the energy more than that band gap -- an electronic-electron hole is used. When making the photocatalytic reaction like the above cause conventionally, usually it was irradiated with light in the state where the photocatalyst had deposited in the shape of a field at the bottom of reaction vessels, such as a beaker thru/or a flask, or it was suspended in solution by operation of stirring etc. The effective catalyst in the case of the former is limited to the portion which exists on the field where irradiation light hits, and the catalyst which exists in an inside from the surface does not contribute to a reaction. In the case of the latter, irradiation light was scattered about by catalyst particles, and since it was lost out of the system of reaction or light volume decreased by the optical absorption by solution, there was inconvenience of not being irradiated with light effective in photocatalyst particles. In the case of above-mentioned both, complicated operation in which ultra filtration membrane, centrifugal separation, or other means separate catalyst particulates from solution was required after the end of a reaction as an industrially important problem.

[Problem which an invention tends to solve] In support of a photocatalyst, the efficiency of the present invention in which light strikes upon catalyst particles is low uneconomical, and an object of the present invention is to solve the problem of the conventional technology that complicated operation of separating catalyst particles from solution is needed after the end of a reaction.

[Means for Solving the Problem] In order to achieve the above-mentioned object, the present invention is a fixed photocatalyst which makes the surface of particles which are the transparent bodies of transparent shape where surface area per unit weight is comparatively large, flakes, or textiles come to cover a thin film of a substance which has photocatalyst activity at least to a light required for activation of the substance at least. In the present invention, platinum, Palladium or a titanium oxide in which an additive agent (photocatalyst catalyst) which consists of Rodiums is added, titanic acid straw Thium, and a cadmium sulfide can be raised as a substance which has photocatalyst activity. For example, a wavelength of a light required for activation of 2 oxidization titanium oxide is about 450 nm, It of titanic acid straw Thium is as particles, flakes, or textiles of a transparent material to about 400 n m and That of a cadmium sulfide, Glass which has 5-mm particle diameter from 10 microns, or particles which comprise material of transparent crystalline material like translucent alumina, 1 micron to delta It is preferred to use textiles of the above-mentioned material with a diameter of Millimeter and flakes of the above-mentioned material which has a thickness of 1 - 10 microns and the maximum width of 5 mm. As for the titanium oxide thin film, it is preferred to contain the additive agent 1.0 to 20% of the weight, this titanium oxide thin film -- 10-300 n m -- a thing in a wavelength band not more than good 6nm which has the transmissivity of at least 50% to a 1-mm-thick material to light of a certain wavelength more preferably than at least 10% at least is used more. The reason for limitation of a diameter of a particle of minerals transparent material which is a photocatalyst carrier of the present invention, a fiber diameter, or a size of flakes is as follows. If the above-mentioned diameter of a particle becomes smaller than 10 microns, after a photocatalytic reaction, separation of a processed liquid and a catalyst will need complicated operation of ultra filtration membrane or centrifugal separation, and will be contrary to soul of the present invention. a diameter of the above should fill up with 1 or more Tarr of 6 Millimeters into fixed capacity -- an effective amount of Photocatalyst decreases and efficiency in which light strikes upon catalyst particles becomes it is low and uneconomical. Shape of particles does not have restriction in particular and a bead, a crushed grain, etc. are used. It is the same as that of a case of particles also about textiles or a reason for limitation in the case of flakes. As for a titanium oxide thin film, it is preferred to have the thickness of 110 to 300 n, and it is preferred to contain the additive agent 1.0 to 20% of the weight. An additive agent of quantity which the additive agent may be uniformly distributed over an inside of a thin film, and is equivalent to the above-mentioned content may be made to adhere on the surface of a thin film.

[Function] Since the photocatalyst of the present invention is supported on the transparent body like glass, irradiation light is not vainly lost by dispersion or absorption, and since photocatalyst activity thin films, such as 2 oxidization titanium, are irradiated repeatedly, it can be used effectively and can separate a photocatalyst from solution easily after the end of a reaction. The photocatalyst of the present invention can also perform 2 operations of a reaction and separation simultaneously by using with the form of a filter because of the above-mentioned feature.

[example Co Since Chita Near to a particle [ of minerals transparent material ] thru/or textiles top thru/or the thin film forming method of platinum belong to known art in itself, below, it is briefly explained as an example to which the present invention is not limited. After putting the particles thru/or textiles of minerals transparent material into containers, such as an alumina crucible, and heating to The 350 in an electric furnace thru/or 800degreeC, Since a thin film with the most simply good dip-coating method heated to 500 thru/or 6deltao'c is formed after the method of supplying into the solution containing Ti, Pt, etc. or the above-mentioned particles thru/or textiles are immersed into the above-mentioned solution, it is desirable. A sol gel process may be adopted as one of the describing [ above ] dip-coating methods. However, the above-mentioned thin film may be formed by the method learned from the former, such as the spraying method, a CVD method, a vacuum evaporation method, and the sputtering method. 2 oxidization titanium usually produces transition to the rutile which is another crystal form from Anatase which is one of the crystal forms above 7006C. A band gap 200-meV-size-comes, and hurts, and the direction of Anatase is rich in oxidization power, and more desirable as a photocatalyst than as rutile. It is desirable to decide suitably according to the kind of coating technology so that it may become temperature that transition to rutile from Anatase does not produce the heating temperature of minerals material for the reason for the above. The result of the example of the present invention is shown in Table 1. Each thickness of 2 oxidization titanium thin film is 200 - 1000 A, and pt contains it about 5% of the weight in 2 oxidization titanium thin film about test number 2-12. In order to judge the effect of the photocatalyst of the present invention, a depth of about 2 cm was filled up with the photocatalyst of the example of Table 1 into the silica glass container into which solution (CH30H1 copy and H2O1 copy) was put. However, only in the case of the silica glass stick, a depth of 8 cm was filled up. Subsequently, a hydrogen yield (ml/hour, and]0-cm2 irradiation area, 25-degree conversion [ C-1 atmosphere ]) when it glares by high-pressure Mercury lamp (400W) is shown in Table 1. The distance of Mercury lamp and a sample was 5 cm. The above-mentioned solution blew nitrogen enough, and after changing into the state where there is no dissolved oxygen, it examined it. Measurement of the hydrogen yield was performed by the gas chromatograph. The thickness of the coated Chita Near thin film was 220-1O0n. For comparison, Example No of Table 1, 1-No, and 3 are what showed the example of the opaque carrier, and they do not belong to the present invention. Solution composition and the method of preparation of solution A-E are as follows. (Durham) A: N-N Si * methyl form 7MidHCON(CIL3)2 100 Acetyl r Ceton crisp Ti0(C6H702)2 1.0 chloro Haenso * Nido 1 fly platinum ptc+. (CsflsCN) 2 100 copies of 0.08B= ethyl alcohol reaches. In the solution of two copies of titanium tetrachloride, the bunch of silica glass textiles is immersed and pulled up, and it dries. After calcinating the above-mentioned textiles for 10 minutes 650-degree Centigrade in an electric furnace, it takes out outside a furnace. Next, the textiles which were used in this way and coated with TiO2 are dipped into 00002% of a palladium chloride, and methyl alcohol 50% of solution, and it irradiates with them for 10 minutes with a high-pressure mercury lamp (400W), and makes palladium deposit to the above-mentioned fiber surface by the optical deposition method. TlO2 dips the textiles by which coaching was carried out into 0.002% of a rhodium chloride, and methyl alcohol 50% of solution, and it makes rhodium deposit by the same operation as B like CAB -- it cheats. D: Ethyl alcohol C2H6 The leaves 100g titanium tetrachloride TiC145g 50 copies of Acetyl acetone platinum Pt(acac) 20.06 gE= ethyl alcohol and 77 copies of titanium tetraisopropoxide are well mixed at room temperature, and this is cooled to O''C, 50 copies of ethyl alcohol 5.0 copies of water, chloride Glass is immersed in the liquid which trickles 0.8 copies and it adds, and glass is pulled up gradually, and it dries, and cools after 500' C-10-minute heating. Light irradiation of this was carried out for 10 minutes by high-pressure Mercury lamp (400W) in 0.002% of platinum chloride acid, and methyl alcohol 50% of solution 11, and optical Debosition was performed.

Effect Co of [invention It is a fixed photocatalyst of the present invention as explained in full detail above, Since a carrier like the particles of minerals transparent material, textiles, a stick, or flakes is fixed while comparable as the conventional particulate photocatalyst or it has an effect per reaction vessel beyond it, Separation with reaction liquid becomes unnecessary, and since a predetermined reaction can be performed only by a substrate passing the reaction apparatus of the present invention, operation becomes very easy. The acetic acid in which the fixed photocatalyst by the present invention is contained underwater, phenol, P. Since organic matters, such as c, e, and organic halogen, and cyanogen ion can be decomposed and processed, it can use for a waterworks and lower effluent treatment thru/or manufacture of ultrapure water. it stand-rare-To-Hg(s) and Cd [ in very small quantities, ] to underwater, -- it can use for recovery of harmful heavy metal ion. Since the oxidization power of the Chita Near photocatalyst is very strong, the bacillus which exists underwater can also be killed. As this example, a living body's W! and work of coenzyme A which is Discard can be stopped and sterilized by Chita Near who did light irradiation. The stinking compound which contains sulfur and nitrogen with a photocatalyst and which carries out a thing can also be disassembled. Table 1 (continuation) Natase powder and (P25)