WO2006030780A1 - 可視光を吸収する薄片状酸化チタンの製造方法 - Google Patents
可視光を吸収する薄片状酸化チタンの製造方法 Download PDFInfo
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- WO2006030780A1 WO2006030780A1 PCT/JP2005/016835 JP2005016835W WO2006030780A1 WO 2006030780 A1 WO2006030780 A1 WO 2006030780A1 JP 2005016835 W JP2005016835 W JP 2005016835W WO 2006030780 A1 WO2006030780 A1 WO 2006030780A1
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- Prior art keywords
- titania
- titanium oxide
- nitrogen
- visible light
- organic
- Prior art date
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 151
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title abstract description 17
- 230000008569 process Effects 0.000 title abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 15
- -1 titanium alkoxide Chemical class 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 150000007942 carboxylates Chemical class 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 16
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 7
- 238000007796 conventional method Methods 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0018—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings uncoated and unlayered plate-like particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Definitions
- the present invention relates to a method for producing flaky titanium oxide for photocatalyst that absorbs visible light.
- a photocatalyst causes charge separation in itself upon irradiation with light, and oxidizes or reduces the partner by giving the generated electrons and / or holes to other substances, that is, photocatalysis. It is a substance that induces various redox reactions.
- the nitrogen-doped titanium oxide reported so far is obtained by heat-treating ordinary titanium oxide for several hours at a high temperature of 500 to 800 ° C in a nitrogen or ammonia stream. Yes.
- Such a high temperature and high nitrogen concentration condition was indispensable for introducing a sufficient amount of nitrogen into the titanium oxide to change the band gap.
- the heat treatment process at such a high temperature generally causes a decrease in the activity of the photocatalyst.
- the photocatalytic reaction is a reaction on the surface of the catalyst, so a high specific surface area is required to achieve high activity S, and the high-temperature heat treatment process for a long time causes the photocatalyst to be densified and dramatically increases the specific surface area. To lower.
- the photocatalytic activity of titanium oxide is greatly influenced by its crystallinity, and in general, the anatase type, which is a quasi-stable type, is said to have the highest activity (Non-patent Document 3).
- the transition to the rutile type which is the most stable crystal form of titanium oxide.
- Patent Document l WO01 / 010552
- Patent Document 4 Japanese Unexamined Patent Publication No. 2003-190809
- Patent Document 5 Japanese Unexamined Patent Publication No. 2003-340288
- Patent Document 6 Japanese Unexamined Patent Application Publication No. 2004-97868
- Non-Patent Document 2 R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science 2001,
- Non-Patent Document 3 K. Kato, A. Tsuzuki, H. Taoda, Y. Torii, T. Kato, Y. Butsugani, J. Mater. Sci. 29 (1994) 5911
- the titanium oxide photocatalyst that has been conventionally driven only by ultraviolet light can be driven by visible light, which is the main component of sunlight.
- the high-temperature heat treatment process necessary for nitrogen doping reduces the original photocatalytic activity of titanium oxide, so that a titanium oxide photocatalyst that can be driven with high efficiency under sunlight can be obtained. Was difficult.
- titanium oxide having a high surface area and a specific surface area is doped with a sufficient amount of nitrogen to exhibit light absorption in the visible light region under mild conditions such as a layer without densification or a rutile transition. If this can be achieved, it can be expected that a titanium oxide photocatalyst that can be driven with extremely high efficiency under sunlight will be obtained, but such a method has not been developed.
- the present invention provides a band gap by a simple and mild chemical technique that does not involve densification, destruction of the structure of the structure, rutile transition, and the phenomenon of reducing the photocatalytic activity of the titanium oxide photocatalyst. It provides a practical and extremely simple chemical synthesis method for doping titanium oxide with a sufficient amount of nitrogen to develop visible light excitation by change.
- the present invention synthesizes a layered titania organic composite having an organic ligand exchangeable with a hydroxyl group between layers, or a titania organic composite having a similar structure by a sol-gel method using a hydrophobic solvent. This is a method for producing flaky titanium oxide for photocatalyst that absorbs visible light, which is obtained by treating this with ammonia water.
- the method of the present invention it is possible to dope titanium oxide with a sufficient amount of nitrogen to exhibit catalytic ability in the visible light region, while providing a tissue structure having a high specific surface area.
- the crystallization state of titanium oxide can be arbitrarily adjusted, it is possible to provide a photocatalyst that can be driven with extremely high efficiency under sunlight.
- the method of the present invention itself is an operation that is extremely simple and under mild conditions, it can be said that the method is highly significant from the viewpoint of industrial productivity and cost.
- a feature of the method of the present invention is that a titania / organic composite obtained by a sol-gel method in which a titanium alkoxide is reacted in a liquid is used as a precursor of a titanium oxide photocatalyst. It is possible to design the size, shape, and structure of the material at the precursor stage. In other words, the process of titania generation and the nitrogen doping process are completely independent. Good for photocatalysts such as small size and high specific surface area It is possible to provide visible light driving characteristics to nitrogen oxide by nitrogen doping while constructing a preferable form in the formation process of titania and further maintaining the form, so that the method of the present invention is compared with the conventional titanium oxide photocatalyst. It can be expected to obtain a highly efficient and highly efficient visible light responsive photocatalyst.
- a titania / organic composite composed of titania and various organic ligands is synthesized by a sol-gel method in which a titanium alkoxide is reacted in a liquid phase to form a precursor, which is immersed in aqueous ammonia.
- the organic ligand is replaced with a hydroxyl group by a ligand exchange reaction, and at the same time, a high concentration of ammonium is introduced between the layers of the titania layered structure.
- a nitrogen-doped titanium oxide photocatalyst capable of driving visible light is provided.
- the titania / organic composite as a precursor can be used in various ways as long as it is a substance in which an organic ligand exchangeable with a hydroxyl group is coordinated with titania. It is particularly desirable to synthesize by the “sol-gel method” in which titanium alkoxide is reacted in a solution, which can be expected to be combined.
- titanium alkoxides include all titanium alkoxides such as titanium ethoxide, titanium methoxide, titanium isopropoxide, and titanium-n-butoxide.
- Various organic solvents can be used as a solvent for the reaction, but the product after titanium alkoxide control of high reactivity and immersion in aqueous ammonia loses the organic ligand and is replaced with a hydroxyl group. Therefore, since it moves from the organic solvent phase to the aqueous phase, it is preferable to use a hydrophobic solvent with a low compatibility with water from the viewpoint of ease of separation of the product and at any time.
- Examples of such substances include various carboxylic acids.
- carboxylate carboxylic acid ion
- titanium alkoxide By mixing carboxylic acid and titanium alkoxide, carboxylate (carboxylic acid ion) is coordinated to titanium alkoxide. After this, by introducing water into the solution, hydrolysis and polycondensation reactions occur, and the titania / carboxylate complex in which carboxylate is coordinated to titania. You can get a body.
- the carboxylic acid is not limited to a specific one, and a plurality of different carboxylic acids may be mixed and used.
- FIG. 1 (A) schematically shows the structure of the layered titaure / carboxylate complex thus obtained.
- Such self-organization by the interaction of organic matter is a phenomenon seen in the synthesis of various inorganic / organic composites other than this method.
- the coordinated carboxylate was replaced with a hydroxyl group, and at the same time, as shown schematically in FIG. Is introduced between layers of the titania layered structure.
- the preferred ammonia water is concentrated ammonia water from room temperature to less than 100 ° C. When the temperature is 100 ° C or higher, ammonia is vaporized from the ammonia water, which is not preferable.
- the ammonia water treatment substance After the ammonia water treatment substance is dried, it is heated, and nitrogen is doped into titania by decomposition of ammonium, and is crystallized into anatase, so that nitrogen is doped and the flakes that can be driven by visible light A titanium oxide photocatalyst can be obtained. If the heating temperature is too low, crystallization into anatase will be insufficient and nitrogen will not be sufficiently incorporated into the titanium oxide grade. On the other hand, if it is too high, densification and crystallization into rutile occur, and the incorporated nitrogen is released, which is also not preferable.
- the heat treatment temperature is preferably 400 ° C or higher and about 500 ° C or lower, which is a temperature region not involving the rutile transition.
- the solving means of the present invention is the force as described above. explain. In order to show the superiority of the present invention, Comparative Examples 1, 2, 3, and 4 are shown.
- the sol comprising a titania / isostearate complex, concentrated aqueous ammonia (28 wt 0/0) and combined mixed and stirred for 2 hours at 60 ° C. After stirring, the aqueous phase portion was taken out with a separatory funnel, and the product was centrifuged and washed with aqueous ammonia five times. The resulting solid was dried at 120 ° C. When the IR absorption spectrum was measured, the absorption peak attributed to isostearate disappeared completely, and a peak attributed to the hydroxyl group appeared instead. A peak attributed to ammonium was also observed (Figure 3b). When XRD was measured, crystallization was not observed and it was a monolayer (Fig. 4a).
- Example 1 The heat treatment temperature of Example 1 was set to 350 ° C. In this case, the specific surface area is 112m 2 g- 1 and strong absorption in the visible light range is also observed (Fig. 5a), but the crystallinity of anatase is lower than that of Example 1 (Fig. 4b) and visible. The photocatalytic ability under light was lower compared to Example 1 (Fig. 7a).
- Example 1 The heat treatment temperature of Example 1 was set to 550 ° C. In this case, although the specific surface area is 7 m 2 g- 1 , which is almost the same as in Example 1, the incorporated nitrogen was released at this heat treatment temperature, and no strong absorption in the visible light range was observed. (Figure 5c). The crystal form was anatase. Figure 4d) The photocatalytic ability under visible light was lower compared to Example 1 ( Figure 7c).
- ST-01 was treated with the same ammonia water and heat treatment as in Example 1, but the carboxylate was not coordinated. ST-01 was not doped with a sufficient amount of nitrogen. Absorption in the strong visible light region as seen in Fig. 5 was not exhibited (Fig. 5e), and the photocatalytic activity under visible light was lower than that in Example 1 (Fig. 7e).
- Titanium oxide doped with nitrogen obtained by the present invention exhibits high photocatalytic activity under visible light irradiation, and can be expected to be a photocatalyst that can be driven with high efficiency under sunlight. Further, according to the production method of the present invention, it is possible to easily produce nitrogen oxide S-doped titanium oxide in which the size, shape, structure, and crystallization state are controlled.
- FIG. 1 is a schematic view showing that a titania / ammonium complex is formed by treating a titania / organic complex with aqueous ammonia in the production method of the present invention.
- FIG. 2 is a drawing-substituting photograph in which the zonore obtained in Example 1 is observed with a scanning electron microscope.
- FIG. 3 shows an IR absorption spectrum (a) of the sol obtained in Example 1 and an IR absorption spectrum (b) after treatment with ammonia water.
- FIG. 4 is an XRD measurement pattern after heating the substance after treatment with aqueous ammonia in Example 1, Comparative Example 1, and Comparative Example 2.
- FIG. 5 is a graph showing the relationship between the wavelength and absorbance of titanium oxide obtained in Example 1 and Comparative Examples 1 to 4.
- FIG. 6 is a drawing-substituting photograph in which the substance after heating in Example 1 is observed with a scanning electron microscope.
- FIG. 7 is a graph showing the results of evaluating the photocatalytic activity of titania of Example 1 and Comparative Examples 1 to 4 under visible light irradiation.
Abstract
Description
Claims
Priority Applications (1)
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US11/662,504 US7651675B2 (en) | 2004-09-13 | 2005-09-13 | Process for producing flaky titanium oxide capable of absorbing visible light |
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JP2004265318A JP4817219B2 (ja) | 2004-09-13 | 2004-09-13 | 可視光を吸収する薄片状酸化チタンの製造方法 |
JP2004-265318 | 2004-09-13 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007238406A (ja) * | 2006-03-10 | 2007-09-20 | Shinshu Univ | 可視光で光触媒能を発現する薄片状窒素ドープ型酸化チタン |
US8017542B2 (en) | 2006-12-13 | 2011-09-13 | Kawamura Institute Of Chemical Research | Method for production of doped titanium oxide, doped titanium oxide, and visible light-responsive photocatalyst comprising the doped titanium oxide |
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WO2009021292A1 (en) * | 2007-08-16 | 2009-02-19 | The University Of Queensland | Titanate photocatalyst |
CN102481565B (zh) * | 2009-06-01 | 2015-03-25 | 新日铁住金株式会社 | 具有可见光响应性且光催化活性优异的钛系材料及其制造方法 |
US20130115308A1 (en) * | 2010-07-13 | 2013-05-09 | Paul Gannon | Doped material |
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US6794065B1 (en) * | 1999-08-05 | 2004-09-21 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalytic material and photocatalytic article |
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- 2004-09-13 JP JP2004265318A patent/JP4817219B2/ja not_active Expired - Fee Related
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2005
- 2005-09-13 US US11/662,504 patent/US7651675B2/en not_active Expired - Fee Related
- 2005-09-13 WO PCT/JP2005/016835 patent/WO2006030780A1/ja not_active Application Discontinuation
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MATSUMOTO D. ET AL: "Sosuiba Sol-Gel-ho ni yoru Sojyo Titania/Carboxylate Nanocomposite Jiritsumaku no Gosei.", THE CERAMIC SOCIETY OF JAPAN NENKAI KOEN YOKOSHU., March 2004 (2004-03-01), pages 41, XP002998891 * |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007238406A (ja) * | 2006-03-10 | 2007-09-20 | Shinshu Univ | 可視光で光触媒能を発現する薄片状窒素ドープ型酸化チタン |
US8017542B2 (en) | 2006-12-13 | 2011-09-13 | Kawamura Institute Of Chemical Research | Method for production of doped titanium oxide, doped titanium oxide, and visible light-responsive photocatalyst comprising the doped titanium oxide |
Also Published As
Publication number | Publication date |
---|---|
US7651675B2 (en) | 2010-01-26 |
JP4817219B2 (ja) | 2011-11-16 |
US20080003153A1 (en) | 2008-01-03 |
JP2006075794A (ja) | 2006-03-23 |
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