WO2012023612A1 - 光触媒皮膜の製造方法及び光触媒皮膜 - Google Patents
光触媒皮膜の製造方法及び光触媒皮膜 Download PDFInfo
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- WO2012023612A1 WO2012023612A1 PCT/JP2011/068784 JP2011068784W WO2012023612A1 WO 2012023612 A1 WO2012023612 A1 WO 2012023612A1 JP 2011068784 W JP2011068784 W JP 2011068784W WO 2012023612 A1 WO2012023612 A1 WO 2012023612A1
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- WIPO (PCT)
- Prior art keywords
- photocatalyst
- slurry
- water
- film
- titanium dioxide
- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 148
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 50
- 239000011248 coating agent Substances 0.000 title abstract description 9
- 238000000576 coating method Methods 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 147
- 239000002002 slurry Substances 0.000 claims abstract description 85
- 229910052742 iron Inorganic materials 0.000 claims abstract description 52
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- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 150000002739 metals Chemical class 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 107
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 4
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 abstract 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 abstract 1
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- 239000011651 chromium Substances 0.000 description 42
- 239000010949 copper Substances 0.000 description 40
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- 238000011156 evaluation Methods 0.000 description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
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- C23C18/127—Preformed particles
Definitions
- the present invention relates to a method for producing a photocatalytic film and a photocatalytic film. Specifically, for example, the present invention relates to a method for producing a photocatalytic film having a photocatalytic function capable of detoxifying, antibacterial, and sterilizing pollutants, and a photocatalytic film.
- the “photocatalytic function” is a catalyst that is excited when irradiated with light energy larger than the band gap energy of its conduction band and valence band, and generates an electron-hole pair to cause oxidation and reduction reactions. This means the function of the substance (photosemiconductor substance).
- photocatalysts in particular, titanium dioxide (TiO 2 ), in particular, photocatalysts using titanium dioxide particles having a rutile-type crystal structure are inexpensive, excellent in chemical stability, and have high catalytic activity. Due to its powerful organic substance-degrading activity, it decomposes bacteria and other harmful substances such as endotoxin that is a cell wall outer wall component of bacteria and toxins produced by bacteria (for example, verotoxin produced by pathogenic Escherichia coli). Moreover, the photocatalyst itself has the advantage that it is harmless to the human body.
- titanium dioxide Since titanium dioxide exhibits photocatalytic activity only under ultraviolet irradiation, it cannot exhibit sufficient catalytic activity under room light containing almost no ultraviolet component. Therefore, a technique is known in which photocatalytic activity is exhibited under visible light irradiation by supporting a metal such as iron or a metal complex or metal salt such as FeCl 3 on titanium dioxide, that is, an iron compound.
- a photocatalyst composition containing titanium dioxide powder carrying a sensitizer is dispersed in, for example, paint, and the like.
- the photocatalyst film was manufactured by coating the surface of the building materials and the like.
- titanium dioxide TiO 2
- FeCl 3 iron chloride
- a photocatalytic composition in which an iron compound is supported on titanium dioxide requires an extremely long time for its processing and manufacturing process, and can improve quality, reduce costs, or stabilize these by shortening the manufacturing process. Was demanded.
- the present invention has been made in view of the above points, and an object of the present invention is to provide a photocatalytic film manufacturing method and a photocatalytic film that can shorten the manufacturing process, have stable quality, and reduce costs. Is.
- a method for producing a photocatalytic film according to the present invention comprises photocatalyst particles and at least one compound selected from a water-soluble metal complex or a water-soluble metal salt of Fe, Cu, Cr, and Ni. Forming a slurry containing water, spraying the slurry, and at least one metal ion of the compound reacts with water to produce hydroxide, oxy of Fe, Cu, Cr, Ni A step of supporting at least one type of hydroxide or oxide on the photocatalyst particles in the slurry and laminating the photocatalyst particles on an object.
- a slurry containing photocatalyst particles at least one compound selected from a water-soluble metal complex of Fe, Cu, Cr, Ni or a water-soluble metal salt, and water, and spraying this slurry , Fe, Cu, Cr, Ni water-soluble metal complexes or metal ions of water-soluble metal salts react with water to form nano-sized very fine Fe, Cu, Cr, Ni hydroxides, oxyoxides or Oxides are generated, and these hydroxides, oxyoxides or oxides are uniformly distributed and supported on the surface of the photocatalyst particles.
- At least one of Fe, Cu, Cr, Ni hydroxides, oxyhydroxides or oxides produced by spraying the slurry and reacting at least one metal ion of the compound with water.
- the hydroxide, oxy of Fe, Cu, Cr, Ni By spraying the slurry without supporting at least one form of hydroxide or oxide on the photocatalyst particles, nano-sized very fine Fe, Cu, Cr, Ni hydroxide, oxyoxide or The oxide is dispersed and supported on the surface of the photocatalyst particles, so that the manufacturing process can be greatly shortened and the performance and quality of the photocatalytic functional film can be stabilized.
- Examples of the “water-soluble metal complex of Fe, Cu, Cr, Ni” include, for example, [Cu (NH 3 ) 4 ] 2+ , [Fe (CN) 6 ] 4 ⁇ , [Fe (CN) 6 ] 3 ⁇ , C 10 H 12 FeN 2 O 8 and the like, and examples of the “water-soluble metal salt of Fe, Cu, Cr, Ni” include, for example, FeCl 3 , Fe 2 (SO 4 ) 3 , Fe (NO 3 ) 3. CuSO 4 , Cu (NO 3 ) 2 , CuCl 2 , Ni (NO 3 ) 2 , NiCl 2 , NiSO 4 , Cr (NO 3 ) 3 and the like.
- examples of “Fe, Cu, Cr, Ni hydroxides, oxyoxides or oxides produced by the reaction of water-soluble metal complexes of Fe, Cu, Cr, and Ni with water” include, for example, CuO, Cu (OH) 2 , FeO (OH), Fe (OH) 3 and the like are mentioned. “Oxidation of Fe, Cu, Cr, Ni produced by reaction of metal salt of Fe, Cu, Cr, Ni with water For example, FeO (OH), Fe (OH) 3 , Cu (OH) 2 , CuO, Ni (OH) 2 , NiO (OH), Cr (OH) 3 , Examples include Cr 2 O (OH) 4 and Cr 2 O 3 .
- the hydroxide, oxyhydroxide or oxide of Fe, Cu, Cr, or Ni exhibits a visible light response function
- the Fe, Cu, Cr, or Ni supported under visible light irradiation the hydroxide, oxyhydroxide, or oxide is excited, and the excited electrons move to the photocatalyst particle side, thereby oxidizing the Fe, Cu, Cr, Ni hydroxide, oxyhydroxide, or oxide surface.
- a reduction reaction occurs on the surface of the reaction and photocatalyst particles, and visible light responsiveness is expressed (see FIG. 1A).
- Fe, Cu, Cr, and Ni hydroxides, oxyhydroxides, or oxides exhibiting a visible light response function are FeO (OH), Fe (OH) 3 , Cu (OH) 2 , CuO, and Ni. (OH) 2, NiO (OH ), Cr (OH) 3, Cr 2 O (OH) 4, Cr 2 O 3 and the like.
- the photocatalyst particles are excited under ultraviolet irradiation, and excited electrons are converted into Fe, Cu, Cr, Oxidation reaction on the surface of photocatalyst particles by moving to the hydroxide, oxyhydroxide or oxide side of Ni, reduction reaction on the hydroxide, oxyhydroxide or oxide surface of Fe, Cu, Cr, Ni As a result, the electrocatalytic performance is improved by the electrification and separation (see FIG. 1B).
- Fe, Cu, Cr, Ni hydroxide, oxyhydroxide or oxide exhibiting a promoter function examples include Fe 2 O 3 , CuO, NiO and the like.
- the method for producing a photocatalytic film according to the present invention comprises a slurry containing photocatalyst particles, at least one compound selected from water-soluble metal complexes or water-soluble metal salts of Fe, Cu, Cr, and Ni, and water. And a step of thermally spraying the slurry and laminating the photocatalyst particles contained in the slurry on an object.
- a slurry containing photocatalyst particles at least one compound selected from a water-soluble metal complex of Fe, Cu, Cr, Ni or a water-soluble metal salt, and water, and spraying this slurry , Fe, Cu, Cr, Ni water-soluble metal complexes or metal ions of water-soluble metal salts react with water to form nano-sized very fine Fe, Cu, Cr, Ni hydroxides, oxyoxides or Oxides are generated, and these hydroxides, oxyoxides or oxides are uniformly distributed and supported on the surface of the photocatalyst particles.
- the hydroxylation of Fe, Cu, Cr, Ni is performed in advance.
- a slurry without supporting photocatalyst particles with at least one form of an oxide, oxyhydroxide or oxide, nano-sized very fine Fe, Cu, Cr, Ni hydroxide, oxy Oxides or oxides are dispersed and supported on the surface of the photocatalyst particles, so that the manufacturing process can be greatly shortened and the performance and quality of the photocatalytic functional film can be stabilized.
- the slurry containing photocatalyst particles such as titanium dioxide further contains at least one of antibacterial metals (for example, silver-based, copper-based, zinc-based, aluminum-based, nickel-based, cobalt-based, or chromium-based metals). ), Containing an antibacterial metal salt or antibacterial metal complex, and spraying a slurry containing the antibacterial metal, antibacterial metal salt or antibacterial metal complex, the antibacterial metal or antibacterial metal complex together with the photocatalyst particles to the metal, metal salt, metal complex, It can be laminated in at least one form selected from oxyhydroxide, hydroxide or oxide, and a photocatalytic functional film having a strong antibacterial action can be produced.
- antibacterial metals for example, silver-based, copper-based, zinc-based, aluminum-based, nickel-based, cobalt-based, or chromium-based metals.
- the photocatalyst particles containing the pigment can be laminated, and a colorful design property can be obtained.
- a high photocatalytic film can be produced.
- an adsorbent can be laminated
- an adsorbent for example, zeolite etc.
- a photocatalytic film having a high gas adsorbing ability can be produced.
- the photocatalyst film according to the present invention comprises photocatalyst particles and at least one compound selected from water-soluble metal complexes or water-soluble metal salts of Fe, Cu, Cr, and Ni.
- Forming a slurry containing water, spraying the slurry, and at least one metal ion of the compound reacts with water to produce hydroxide, oxyhydroxide of Fe, Cu, Cr, Ni
- at least one type of oxide was supported on the photocatalyst particles in the slurry, and the photocatalyst particles were laminated on the object.
- the photocatalyst film according to the present invention forms a slurry containing photocatalyst particles, at least one compound selected from water-soluble metal complexes or water-soluble metal salts of Fe, Cu, Cr, Ni, and water, The slurry was sprayed, and the photocatalyst particles contained in the slurry were laminated on the object to be manufactured.
- objects to be laminated with photocatalyst particles tiles, sanitary ware, glass, mirrors, concrete building materials, resin building materials, metal building materials, resin films, metal fibers, glass fibers, carbon fibers, these Examples thereof include a filter using fibers.
- the photocatalytic film can be produced by a greatly shortened production process, so that the quality and performance of the film are small and high quality and production yield can be realized. Also, high quality can be achieved for the photocatalytic film to which the present invention is applied.
- An example of a method for producing a photocatalytic film to which the present invention is applied consists of two processes: (1) a water slurry generation process and (2) a thermal spray coating formation process. Hereinafter, each process will be described in detail.
- a water slurry using a rutile type titanium dioxide powder having a particle size of about 30 nm and an aqueous iron chloride solution is generated.
- the rutile type titanium dioxide powder is aggregated to have a particle size of about 1 ⁇ m to 5 ⁇ m.
- the photocatalyst particles are not necessarily titanium dioxide particles.
- tungsten oxide or Tin oxide or the like may be used.
- titanium dioxide it is preferable to employ titanium dioxide as a photocatalyst in consideration of the low cost, excellent chemical stability, and high catalytic activity.
- iron chloride (FeCl 3 ) that is, a case where a water-soluble metal salt of iron (Fe) is used as an example of the sensitizer is described as an example.
- a water-soluble metal salt or water-soluble metal complex of iron (Fe) is used as an example of the sensitizer.
- Table 1 shows the titanium oxide crystal strength count by XRD measurement when the water slurry concentration is 10% by weight and when it is 30% by weight. Note that “titanium oxide crystal strength count” indicates the adhesion rate (presence rate) of the material.
- concentration is 30 weight%.
- a spraying temperature variable type high-speed thermal spraying apparatus described in JP-A-2005-68457 can be used.
- a photocatalyst film is formed by pumping the generated water slurry to a high-speed flame (frame) blown out from a spray gun by combustion of oxygen and kerosene, and colliding with a target substrate at high speed.
- the amount of oxygen used is reduced and the flame (frame) is further accelerated.
- the spraying temperature conditions are a flame (frame) temperature of 700 to 2500 ° C. and a spraying speed of 800 to 2000 m / sec. It is.
- the average temperature is set as the flame (frame) temperature.
- the temperature is measured without adding water slurry and mixing air, and using a thermocouple (for example, a SUS material up to about 1000 ° C., otherwise a thermocouple of tungsten / rhenium (WW ⁇ Re)). Used in contact with flame. The same applies to these points.
- FIG. 3 shows the result of analysis of the crystal structure using an X-ray diffractometer (XRD) of the photocatalyst film obtained by the method for producing the photocatalyst film to which the present invention is applied.
- XRD X-ray diffractometer
- FIG. 4 shows the analysis result of the crystal structure using XRD of the photocatalyst film obtained by the conventional photocatalyst film production method.
- the mixture was stirred for 2 hours, and Fe was supported on the TiO 2 powder.
- the solution was dried and pulverized, and then the particle size was classified to adjust the particle size to about 100 ⁇ m.
- thermal spraying was performed using the prepared aqueous slurry of powder (concentration 30% by weight) to form a photocatalyst film, and the crystal structure of the photocatalyst film thus obtained was analyzed by XRD. is there.
- Such a photocatalytic film manufacturing method is referred to as a “pre-supporting method” for convenience.
- pre-supporting method that is, titanium dioxide (TiO 2 ) is preliminarily immersed and stirred in an aqueous solution of iron chloride (FeCl 3 ) serving as a sensitizer, and iron or an iron compound is supported on titanium dioxide.
- iron chloride FeCl 3
- the treatment takes a long time and a drying process may be performed. During this time, the iron and iron compounds supported on the titanium dioxide surface are aggregated and grown. It is highly likely that segregation or the like occurs.
- the sensitizer and the antibacterial metal compound are dissolved at the molecular level is instantaneously immobilized on the titanium dioxide surface by thermal spraying, the sensitizer and the antibacterial metal compound are nano-sized. It is thought that it is dispersed and supported on the surface of titanium dioxide.
- the sensitizer and antibacterial metal compound of the present invention are extremely dispersible as compared with the prior art, it is considered that a higher sensitization effect and antibacterial effect than expected can be obtained.
- the Cl component could be confirmed from the result of the electron micrograph using SEM-EDS of the photocatalyst film obtained by the pre-loading method, the element component analysis, and the element distribution analysis. This is considered to be due to the influence of FeCl 3 used when Fe is supported. That is, it is considered that Cl forms some compound at the time of loading and does not volatilize due to the heat of spraying, and there is a concern that the photocatalytic properties of the photocatalytic film may be deteriorated due to contamination of such impurities.
- the EDS analysis result of the photocatalyst film obtained by the pre-supporting method is shown in Table 2a.
- FIG. 5 shows the analysis result of the crystal structure using XRD of the photocatalytic film obtained by supporting iron after the formation of the titanium dioxide film.
- FIG. 5 shows the result of analyzing the crystal structure of the photocatalyst film thus obtained by XRD by immersing it in an FeCl 3 solution for 2 hours so as to be 99: 1 and supporting Fe on the TiO 2 film.
- a post-carrying method Such a method for producing a photocatalytic film is referred to as a “post-carrying method” for convenience.
- the ratio of Ti and Fe was obtained by the present invention and the pre-supporting method. It was found to be higher than the photocatalytic film obtained. This is presumably because Fe was segregated on the analysis surface due to the characteristics of the post-carrying method in which Fe was carried on the film surface. In such a case, when the coating is worn, there is a concern that the lifetime of the visible light response characteristic is short because Fe does not exist inside the coating.
- the EDS analysis result of the photocatalyst film obtained by the post-carrying method is shown in c of Table 2.
- titanium dioxide powder having a rutile crystal structure which is cheaper than an anatase crystal structure, is used, and cost reduction is realized.
- FIG. 6 shows a conceptual diagram of the evaluation test method.
- the test piece of the sprayed coating used for the evaluation has a size of about 50 mm square, and a porcelain tile is used as the base material.
- the surface of the test piece was washed with alcohol in advance and pretreated by irradiating with ultraviolet rays (ultraviolet light intensity: 1 mW / cm 2 ) for 12 hours, and used for the gas decomposition evaluation test.
- ultraviolet rays ultraviolet rays
- the target gas for decomposition was acetaldehyde, which was adjusted to about 450 ppm in a Tedlar bag (125 cc).
- An LED light (wavelength 415 nm) was used as a light source, and the film surface of the sample was irradiated with a light intensity of 6 mW / cm 2 .
- the samples tested were a photocatalyst film obtained by a method for producing a photocatalyst film to which the present invention was applied and a photocatalyst film obtained by a post-carrying method.
- the test was also conducted on a commercially available photocatalytic tile and a sulfur-doped titanium oxide sprayed coating that is a visible light type photocatalyst.
- FIGS. 7 and 8 The results of the acetaldehyde gas decomposition test of each film are shown in FIGS. 7 and 8, it can be seen that the photocatalytic film obtained by the method for producing a photocatalytic film to which the present invention is applied exhibits high acetaldehyde gas decomposition activity. In addition, about twice the amount of acetaldehyde is observed with carbon dioxide, and it is considered that complete decomposition has been performed.
- the photocatalytic film obtained by the post-loading method showed the same gas removal performance as compared with the sulfur-doped titanium oxide.
- the amount of carbon dioxide generated was small compared to the photocatalyst film obtained by the method for producing a photocatalyst film to which the present invention was applied, and after the test, there was a sour odor that seemed to be an intermediate product. Therefore, it is presumed that the gas decomposition reaction in this case was not complete.
- the result of the gas decomposition test performed on the commercially available photocatalytic tile showed a considerably low decomposition activity as compared with the photocatalyst film obtained by the photocatalyst film production method to which the present invention was applied.
- FIG. 9 shows a conceptual diagram of the evaluation test method.
- the test piece of the thermal spray coating used for the evaluation has a size of about 50 mm square, and a ceramic tile is used as the base material.
- the surface of the test piece was washed with acetone and pretreated by irradiating with ultraviolet rays (ultraviolet intensity: 1 mW / cm 2 ) for 6 hours, and subjected to an antibacterial activity evaluation test.
- each sample was placed in a petri dish (diameter 90 mm), 30 ml of E. coli suspension was added, and this was left standing at 30 ° C. under irradiation conditions (illuminance 1700 lux) with a fluorescent lamp. Thereafter, the number of remaining bacteria was measured over time. The number of bacteria was measured by the colony count method.
- the samples evaluated are a photocatalyst film obtained by a method for producing a photocatalyst film to which the present invention is applied, a sulfur-doped titanium oxide film, and a commercially available photocatalytic tile.
- the evaluation test results are shown in FIG.
- the sterilizing power of the photocatalyst film obtained by the photocatalyst film manufacturing method to which the present invention is applied to Escherichia coli decreases by 4 orders in 30 minutes, and shows high sterilization characteristics of sterilizing all 6 orders in 180 minutes. I understand. Although it did not reach the 6-order sterilization power seen in this point and the sulfur dope titanium oxide in 30 minutes, it can be said that it has sufficient performance for practical use. In addition, even if the commercially available photocatalyst tile compared with the blank, the viable count was hardly decreased and the performance was low.
- a water slurry using a rutile type titanium dioxide powder and an aqueous iron chloride solution is generated.
- water using an anatase type titanium dioxide powder and an aqueous iron chloride solution is produced.
- a slurry may be produced.
- a water slurry using anatase-type titanium dioxide powder having a particle diameter of about 10 nm and an aqueous iron chloride solution may be generated.
- the anatase-type titanium dioxide powder aggregates in the water slurry to have a particle size of about 1 ⁇ m to 5 ⁇ m.
- a water slurry using anatase-type titanium dioxide powder having a particle size of about 10 nm and an aqueous iron chloride solution is generated (in this case, the anatase-type titanium dioxide powder aggregates in the water slurry to 1 ⁇ m.
- the photocatalyst film is formed by laminating anatase-type titanium dioxide supporting Fe 2 O 3 that performs thermal spraying using the generated water slurry and exhibits a promoter function. You may do it.
- the spraying temperature conditions in this case are flame (flame) temperature of 300 to 2000 ° C. and spraying speed of 800 to 2000 m / sec. It is.
- anatase type titanium dioxide can exhibit higher catalytic activity than rutile type titanium dioxide.
- the used water slurry (concentration 30% by weight) may be generated, and the generated water slurry may be sprayed to form a photocatalyst film.
- a silver oxide (AgO 2 ) which is a kind of antibacterial metal, is supported on a rutile type titanium dioxide film having a visible light response function and a cocatalyst function. If it is applied to floor materials, wall materials, ceiling materials and incidental facilities in hospitals, elderly care facilities, food processing factories and other facilities where hygiene is important, it is possible to have extremely high antibacterial functions. It is effective in preventing infection and food poisoning.
- the nanosized silver oxide was dispersed almost uniformly without segregation. I found out. In addition, it becomes possible to show the stable antibacterial effect because silver oxide disperses substantially uniformly.
- Ti in Fe component weight ratio of Ti component and aqueous solution of iron chloride of titanium dioxide powder (TiO 2) (FeCl 3) : Fe 99.7: FeCl the TiO 2 powder as a 0.3
- Fe 99.7: FeCl the TiO 2 powder as a 0.3
- Ag was further supported on the TiO 2 powder.
- the solution was dried, and after pulverization, the particle size was classified to uniform the particle size. Subsequently, thermal spraying was performed using the prepared aqueous slurry of powder (concentration: 30% by weight) to form a photocatalyst film, and the surface of the photocatalyst film thus obtained was observed using SEM-EDS.
- FIG. 13 shows the analysis result of the crystal structure by XRD of the photocatalyst film formed by thermal spraying using the generated water slurry.
- FIG. 14 shows the analysis result of the crystal structure using XRD of the photocatalyst film obtained by the pre-loading method.
- pellets obtained by mixing both powders such that the Ti component of the titanium dioxide powder (TiO 2 ) and the pigment are in a weight ratio of Ti: pigment 7: 3 and firing at 1200 ° C. for 30 minutes.
- thermal spraying was performed using the prepared aqueous slurry of powder (concentration: 30% by weight) to form a photocatalyst, and the result of analyzing the crystal structure of the photocatalyst film thus obtained by XRD is shown in FIG. .
- the pigment component Fe is Ti. It was found to be about 16%, and the pigment yield was high. This is presumably because the mass of the particles increased due to the combination of the pigment and TiO 2 .
- FIG. 15 shows the analysis result of the crystal structure using XRD of the photocatalytic film obtained by the post-supporting method.
- thermal spraying is performed using a water slurry (concentration 30% by weight) of titanium dioxide powder (TiO 2 ) to form a TiO 2 film.
- TiO 2 titanium dioxide powder
- thermal spraying is performed using a water slurry (concentration 30% by weight) of titanium dioxide powder (TiO 2 ) to form a TiO 2 film.
- the composite structure of TiO 2 and the pigment obtained by baking at 1250 ° C. for 1 hour is analyzed for crystal structure by XRD. The results obtained are shown in FIG.
- the TiO 2 peak disappears, and it is considered that the pigment covered the surface more than the penetration depth of X-rays.
- the ratio of Ti is very low from the electron micrograph using SEM-EDS of the photocatalyst film obtained by the above-mentioned post-loading method and the results of elemental component analysis and elemental distribution analysis (not shown). It was found that the surface was completely covered with the pigment. Due to these pigments, the light intensity reaching the titanium dioxide is lowered, and there is a concern that the photocatalytic function is lowered.
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Abstract
Description
本発明を適用した光触媒皮膜の製造方法の一例では、(1)水スラリー生成プロセス、(2)溶射皮膜形成プロセスの2つのプロセスで成り立っている。以下、各プロセスについて詳細に説明を行う。
本発明を適用した光触媒皮膜の製造方法の一例では、二酸化チタン粉末(TiO2)のTi成分と塩化鉄水溶液(FeCl3)のFe成分が重量比でTi:Fe=99:1となる様に、二酸化チタン粉末と塩化鉄水溶液を用いた水スラリー(濃度30重量%)を生成する。
本発明を適用した光触媒皮膜の製造方法の一例では、続いて、生成した水スラリーを用いて溶射を行って光触媒皮膜を成膜する。
これに対して、本発明を適用した光触媒皮膜の製造方法で得られる光触媒皮膜では、こうした不具合が生じることが無く、可視光応答性に優れると共に可視光応答性の長寿命化が実現する。
図6に評価試験方法の概念図を示す。評価に用いた溶射皮膜の試験片は約50mm角のサイズで、基材には磁器タイルを用いた。試験片は表面を予めアルコールで洗浄し、紫外線(紫外線強度:1mW/cm2)を12時間照射する前処理を施して、ガス分解の評価試験に用いた。
図7及び図8から、本発明を適用した光触媒皮膜の製造方法で得られる光触媒皮膜は高いアセトアルデヒドガス分解活性を示すことが分かる。また、二酸化炭素についてもアセトアルデヒドの約2倍量の発生が見られ、完全分解が行われていると考えられる。
図9に評価試験方法の概念図を示す。評価に用いた溶射皮膜の試験片は、約50mm角のサイズで、基材には磁器タイルを用いた。試験片は表面をアセトン洗浄し、紫外線(紫外線強度:1mW/cm2)を6時間照射する前処理を施して、抗菌活性の評価試験に供した。
上記した本発明を適用した光触媒皮膜の製造方法では、ルチル型の二酸化チタン粉末と塩化鉄水溶液を用いた水スラリーを生成しているが、アナターゼ型の二酸化チタン粉末と塩化鉄水溶液を用いた水スラリーを生成しても良い。具体的には、例えば、粒径が10nm程度のアナターゼ型の二酸化チタン粉末と塩化鉄水溶液を用いた水スラリーを生成しても良い。なお、この際、水スラリー中ではアナターゼ型の二酸化チタン粉末は凝集して1μm~5μm程度の粒径をなしている。
上記した本発明を適用した光触媒皮膜の製造方法では、ルチル型の二酸化チタン粉末に可視光応答機能を呈するFeO(OH)を担持し、可視光応答型光触媒皮膜を実現する場合を例に挙げて説明を行っている。
しかしながら、光触媒粒子に担持するのは可視光応答機能を呈するものに限定される必要はなく、助触媒機能を呈するFe2O3等であっても良い。
上記した本発明を適用した光触媒皮膜の製造方法の一例では、二酸化チタン粉末と塩化鉄水溶液を用いた水スラリーを用いて溶射を行うことで、鉄の酸化物、水酸化物、オキシ水酸化物の少なくとも1種類の形態が担持した二酸化チタン皮膜を成膜する場合を例に挙げて説明を行っているが、鉄のみならず銀の酸化物、水酸化物、オキシ水酸化物の少なくとも1種類の形態をも担持した二酸化チタン皮膜を成膜しても良い。
また、皮膜表層に厚い銀の偏析の存在が確認でき、こうした表層の銀の偏析に起因して二酸化チタンに到達する光強度が低下してしまい、光触媒性能の低下が懸念される。
上記した本発明を適用した光触媒皮膜の製造方法の一例では、二酸化チタン粉末と塩化鉄水溶液を用いた水スラリーを用いて溶射を行うことで、鉄が担持した二酸化チタン皮膜を成膜する場合を例に挙げて説明を行っているが、鉄のみならず顔料をも担持した二酸化チタン皮膜を成膜しても良い。なお、顔料を担持させることによって光触媒皮膜を着色することができ、顔料の付着量の度合いによって色合いに変化が生じることとなる。
Claims (9)
- 光触媒粒子と、Fe,Cu,Cr,Niの水溶性金属錯体または水溶性金属塩から選ばれる少なくとも1種類の化合物と、水とを含むスラリーを形成する工程と、
前記スラリーを溶射して、少なくとも1種類の前記化合物の金属イオンが水と反応して生成されたFe,Cu,Cr,Niの水酸化物、オキシ水酸化物若しくは酸化物の少なくとも1種類の形態を前記スラリー中の光触媒粒子に担持させると共に、同光触媒粒子を対象物に積層する工程とを備える
光触媒皮膜の製造方法。 - Fe,Cu,Cr,Niの水酸化物、オキシ水酸化物若しくは酸化物が、可視光応答機能を呈する
請求項1に記載の光触媒皮膜の製造方法。 - 前記光触媒粒子が、ルチル型二酸化チタン粒子である
請求項1または請求項2に記載の光触媒皮膜の製造方法。 - 抗菌金属、抗菌金属塩または抗菌金属錯体から選ばれる少なくとも一種類を含んで前記スラリーを形成し、
前記スラリーを溶射して、前記光触媒粒子と共に前記抗菌金属、抗菌金属塩または抗菌金属錯体を、金属、金属塩、金属錯体、オキシ水酸化物、水酸化物、または、酸化物から選ばれる少なくとも一種類の形態で対象物に積層する
請求項1、請求項2または請求項3に記載の光触媒皮膜の製造方法。 - 顔料を含んで前記スラリーを形成し、
前記スラリーを溶射して、前記光触媒粒子と共に顔料を対象物に積層する
請求項1、請求項2または請求項3に記載の光触媒皮膜の製造方法。 - 吸着材を含んで前記スラリーを形成し、
前記スラリーを溶射して、前記光触媒粒子と共に吸着材を対象物に積層する
請求項1、請求項2または請求項3に記載の光触媒皮膜の製造方法。 - 光触媒粒子と、Fe,Cu,Cr,Niの水溶性金属錯体または水溶性金属塩から選ばれる少なくとも1種類の化合物と、水とを含むスラリーを形成する工程と、
前記スラリーを溶射して、同スラリー中に含まれている光触媒粒子を対象物に積層する工程とを備える
光触媒皮膜の製造方法。 - 光触媒粒子と、Fe,Cu,Cr,Niの水溶性金属錯体または水溶性金属塩から選ばれる少なくとも1種類の化合物と、水とを含むスラリーを形成し、
前記スラリーを溶射して、少なくとも1種類の前記化合物の金属イオンが水と反応して生成されたFe,Cu,Cr,Niの水酸化物、オキシ水酸化物若しくは酸化物の少なくとも1種類の形態を前記スラリー中の光触媒粒子に担持させると共に、同光触媒粒子を対象物に積層して製造された
光触媒皮膜。 - 光触媒粒子と、Fe,Cu,Cr,Niの水溶性金属錯体または水溶性金属塩から選ばれる少なくとも1種類の化合物と、水とを含むスラリーを形成し、
前記スラリーを溶射して、同スラリー中に含まれている光触媒粒子を対象物に積層して製造された
光触媒皮膜。
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