WO1998023374A1 - Photocatalyseur ayant une activite lumineuse visible et utilisation de ce dernier - Google Patents
Photocatalyseur ayant une activite lumineuse visible et utilisation de ce dernier Download PDFInfo
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- WO1998023374A1 WO1998023374A1 PCT/JP1997/004191 JP9704191W WO9823374A1 WO 1998023374 A1 WO1998023374 A1 WO 1998023374A1 JP 9704191 W JP9704191 W JP 9704191W WO 9823374 A1 WO9823374 A1 WO 9823374A1
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- Prior art keywords
- photocatalyst
- tic
- light
- visible light
- plasma
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 83
- 230000000694 effects Effects 0.000 title claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 21
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 6
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 230000001699 photocatalysis Effects 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 25
- 238000001069 Raman spectroscopy Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000002411 thermogravimetry Methods 0.000 claims description 13
- 238000004455 differential thermal analysis Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 7
- 238000005452 bending Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000020169 heat generation Effects 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 241000894006 Bacteria Species 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
- 235000017274 Diospyros sandwicensis Nutrition 0.000 claims 1
- 241000282838 Lama Species 0.000 claims 1
- 230000010748 Photoabsorption Effects 0.000 claims 1
- 230000015843 photosynthesis, light reaction Effects 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 150000002894 organic compounds Chemical class 0.000 abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 52
- 210000002381 plasma Anatomy 0.000 description 29
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 17
- 238000000354 decomposition reaction Methods 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- -1 acetate aldehyde Chemical class 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000009832 plasma treatment Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 208000037998 chronic venous disease Diseases 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 235000019833 protease Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 108010085603 SFLLRNPND Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
Definitions
- the present invention relates to a photocatalyst having visible light activity and a photodecomposition method using the catalyst and using light containing visible light.
- W094Z11092 discloses an air treatment method using a photocatalyst under indoor lighting.
- Japanese Patent Application Laid-Open No. 7-120678 discloses a method for preventing hospital-acquired infection using a photocatalyst.
- an oxide semiconductor such as titanium oxide is used as a photocatalyst, and an ultraviolet ray of 40 Onm or less is required as excitation light.
- sunlight and artificial light which serve as excitation light sources, include visible light in addition to ultraviolet light.
- the photocatalyst made of an oxide semiconductor such as titanium oxide does not use visible light, and is very inefficient from the viewpoint of energy conversion efficiency.
- adsorbent In order to remove trace amounts of organic compounds such as formaldehyde in the living environment, it is conceivable to use, for example, an adsorbent.
- adsorbents cannot be said to be sufficient, given their strength, life and adsorption capacity. Therefore, it is expected to provide a new technology that can remove formaldehyde and the like present in trace amounts in the living environment more effectively.
- tar generated from tobacco adheres to, for example, walls, electric lights, window glasses, etc., and deteriorates their appearance.
- Conventionally, such tar and the like have been removed by washing or the like. But the effort is immense. Therefore, it is expected to provide a new technology that can easily remove tar and the like attached to walls, lights, window glasses, and the like.
- a first object of the present invention is to provide a new photocatalyst that can also use visible light.
- a second object of the present invention is to provide a photocatalyst capable of detoxifying an organic compound such as formaldehyde and a method for detoxifying an organic compound such as formaldehyde using such a photocatalyst.
- a third object of the present invention is to provide a method for photolytically removing various substances including organic substances such as evening water by using the photocatalyst.
- the present invention relates to a photocatalyst having the visible light activity, wherein the carrying TiC at least a portion of the Ti0 2 surfaces.
- the photocatalyst of the present invention also has visible light activity, characterized in that the photocatalyst is made of TiO 2 which has been subjected to CVD treatment with a mixed gas of a hydrocarbon and a reducing agent in plasma.
- the present invention relates to a photocatalytic unit characterized in that the catalyst of the present invention is supported on a substrate.
- the TiC at least a portion of the Ti0 2 surfaces which comprises treating a mixed gas of Ti0 2 powder, or immobilized to a substrate Ti0 2 the plasma state coal hydrogen as a reducing agent
- the present invention relates to a method for producing the visible light-excited photocatalyst according to the present invention, which is characterized by being carried.
- the present invention provides the photocatalyst of the present invention, which is irradiated with light containing at least visible light.
- the present invention relates to a method for decomposing a substance, which comprises contacting a substance to be decomposed with a catalyst layer of a photocatalytic unit.
- the present invention relates to a method for decomposing formaldehyde, which comprises contacting formaldehyde with a photocatalyst or a catalyst layer of a photocatalytic unit of the present invention irradiated with light containing at least visible light.
- the present invention relates to a device including the photocatalytic unit of the present invention, wherein the device comprises a water purifying device, an air purifying device, a sterilizing device, a deodorizing device, a lighting device, a photovoltaic cell, and a water photolytic device.
- the device comprises a water purifying device, an air purifying device, a sterilizing device, a deodorizing device, a lighting device, a photovoltaic cell, and a water photolytic device.
- FIG. 1 is a schematic explanatory view of a microphone mouth-wave plasma heating apparatus used in the present invention.
- FIG. 2 is a schematic explanatory view of a high-frequency plasma heating device used in the present invention.
- FIG. 3 is an XPS spectrum of titania and titanium carbide in the photocatalyst of the present invention.
- FIG. 4 shows Raman absorption spectra of titania, hydrogen reduced titania, and the photocatalyst of the present invention.
- FIG. 5 is a diagram showing the relationship between the light irradiation time and the formaldehyde concentration in Example 6.
- FIG. 6 is a diagram showing the relationship between the light irradiation time and the acetate aldehyde concentration in Example 11;
- FIG. 7 is a diagram showing the relationship between the light irradiation time and the acetate aldehyde concentration in Example 13. MODES FOR CARRYING OUT THE INVENTION
- Photocatalyst with visible light activity of the present invention is obtained by carrying TiC at least a portion of the Ti0 2 surfaces, for example, in the plasma, by CVD processes Ti0 2 in a mixed gas of a hydrocarbon as a reducing agent can get.
- Loading amount of TiC to ti0 2 surface is obtained Considering the activity of the photocatalyst, the binding energy scan Bae-vector obtained by X-ray photoelectron spectroscopy, the 4 5 8. Peak height at 5 e V and TiC binding energy of Ti2p3 / 2 attributed to Ti0 2 It is suitable from the viewpoint of having visible light activity that the ratio of the peak height at 450 eV to be assigned is in the range of 100: 1 to 50.
- the amount of TiC supported is preferably such that the ratio of the peak height of 458.5 eV to the peak height of 450 eV is in the range of 100: 1 to 20. Note that there is a correlation between the amount of TiC carried and the visible light activity and ultraviolet light activity, and it is preferable to change the amount of TiC carried according to desired physical properties.
- a photocatalyst having a visible light activity of the present invention is obtained by carrying TiC at least a portion of the Ti0 2 surface, Raman absorption attributed to Ti0 stretch and 0- Ti0 deformation vibration the 0 LOOOcm- either have one or essentially no, and a Raman absorption attributed to Ti C to 3000 ⁇ 3500Cm- 1.
- a Raman absorption present in 0 lOOOcnr 1 attributed to the Ti0 stretch and O-Ti0 bending vibration its intensity, weak it is characterized as compared with Ti0 2 before the CVD process is there.
- the Ti0 stretch and 0 - Raman absorption intensity present in Ti -0 0 lOOOcnT 1 attributed to the deformation vibration is 1 Z 5 following Ti0 2 of intensity before CVD process.
- the intensity is stable over time, and If no absorption, Ti0 stretch and 0 - Ti -0 occurs with the passage of the Raman absorption time due to bending vibration, it does not become Ti0 2 with the same level of pretreatment.
- “stable over time” means that there is no substantial change in the Raman absorption intensity for at least one month, even if left in the air.
- the photocatalyst of the present invention preferably has a Raman absorption intensity existing at 0 to 1000 cnr 1 attributed to Ti-O stretching and 0-Ti-0 bending vibration, which is stable with time, and Ti0 before CVD treatment.
- the peak height at 48.5 eV which is the binding energy of Ti2p3 / 2 obtained by X-ray photoelectron spectroscopy, which is less than 1 Z5 of the intensity of 2, and the peak at 45.5 eV assigned to TiC Substances with a high ratio of 100: 1 to 50.
- TiC + 20 2 - Ti0 2 + CO thermal behavior of the reaction will vary with Atsushi Nobori speed of the particle size Ya surface state or the like and a differential thermal analysis of the sample analysis which is the subject (DTA), generally from about Starting at 300 ° C, the progress becomes remarkable from a temperature of around 500 ° C and progresses to a temperature range of around 1000 ° C.
- Differential thermal analysis (DTA) of the TiC reagent shows an exothermic peak near 500 ° C, and further exothermic in the region exceeding 700 ° C. In particular, heat generation in the region exceeding 700 ° C is remarkably large.
- thermogravimetric analysis at least in a temperature range of more than 5 0 ° C, that the weight increase due to the reaction of the Ti0 2 of TiC is observed is there.
- thermogravimetric analysis (TGA) of the TiC reagent weight increase starts at a temperature around 300 ° C. due to the above reaction, and weight increase is remarkably observed from a temperature around 500 ° C. Especially in the region exceeding 700 ° C, the reaction proceeds rapidly, so that the weight increases significantly.
- thermogravimetric analysis TGA
- the weight increase was small due to the relatively small amount of TiC in the sample, and in the case of low sensitivity, the weight was almost negligible. Only an increase is observed. However, when sensitivity is high, a weight increase is observed. Further, from the increase in weight, it is also possible to some extent quantified TiC carried on Ti0 2 surface. Furthermore, as described above, there is a correlation between the amount of TiC supported and the activities of visible light and ultraviolet light, and it is preferable to change the amount of TiC supported according to desired physical properties. It is also possible to adjust the loading of TiC based on the results of thermogravimetric analysis (TGA).
- Photocatalyst of the present invention more specifically, Ti0 2 powder or vessel containing immobilized Ti0 2 on the substrate under atmospheric pressure or under reduced pressure, reduction of hydrocarbons and water arsenide methane or the like Burazuma of A mixed gas with the agent is supplied, or the mixed gas is plasmanized in the container.
- a mixed gas with the agent is supplied, or the mixed gas is plasmanized in the container.
- plasma conversion for example, high-frequency plasma or microwave plasma may be used, or these plasmas may be used in combination.
- the container can be rotated to process the TiO 2 powder while stirring. More specifically, by irradiating an electromagnetic wave to generate plasma, replacing and Case child oxygen carbon and Ti0 2 in the powder obtained by decomposing methane which is supplied by the plasma in the Ti0 2 powder To make carbide adhere to the surface of the powder particles. Accordingly, the photocatalyst of the present invention carrying TiC at least a portion of the Ti0 2 surfaces are obtained.
- Stirring ti0 2 powder is plasma uniformly irradiate the individual powder particles, it is appropriate to carry out under such conditions that Koti ing a uniform carbide is performed.
- the vessel containing the Ti0 2 powder for example, by rotating in every minute 0-2 0 0 times velocity, plasma powder particles Irradiation is even and uniform carbide coatings can be applied.
- Ti0 2 immobilized on a substrate when processing Ti0 2 immobilized on a substrate, as Ti0 2 of the substrate is uniformly processed, it can also be processed while moving the substrate.
- the degree of vacuum for the CVD process varies depending on the type of plasma. However, in consideration of the ease of plasma generation and the generation rate of TiC, for example, a range of 0.01 to 100 Suitably, it is in the range of 0.1 to 10 Torr.
- the frequency of the electromagnetic wave to be irradiated can be appropriately determined in consideration of the type of the hydrocarbon used, the physical properties of the TiC to be carried, and the like, and can be, for example, in the range of 10 ⁇ to 10 GHz.
- methane is also used as the hydrocarbon, it is appropriate to set the frequency of the electromagnetic wave in the range of 10 MHz to 4 GHz from the viewpoint of efficiently decomposing methane to obtain a TiC coating.
- Microwaves and high frequencies as electromagnetic waves Preferably, it is used.
- Ti0 2 used as a raw material for example, anatase type, but cut with be a rutile type or the like, from the viewpoint of solar energy use, it is appropriate that a Ti0 2 ANATA one peptidase type.
- the particle size of the Ti02 powder is preferably fine particles from the viewpoint of high surface area and high photocatalytic activity.However, considering the easiness of handling, it is, for example, 0.1 to 20 . Suitably, it is in the range of 0 zm.
- Ti0 2 is divalent or more ions, e.g., vanadium, chromium, tungsten, niobium, zinc, Jirukonia, iron, tantalum, high light activity than that force ⁇ is obtained by de one up the tin Is preferred.
- ions e.g., vanadium, chromium, tungsten, niobium, zinc, Jirukonia, iron, tantalum
- the Ti0 2 powder treated in this invention for example, an electromagnetic wave-flop plasma heating device equipment configuration shown in FIG. 1 is used.
- the electromagnetic wave oscillated from the electromagnetic wave oscillator 1 is sent out through the isolator 2 and the output is measured by the power monitor 3. Next, it is sent into the reaction chamber 5 through the three-stub tuner 4.
- a plunger 6 is provided below the reaction chamber 5. Above the plunger 6, a quartz reaction tube 7 containing the powder to be treated is arranged. The quartz reaction tube 7 is rotatable by a star 8. The inside of the quartz reaction tube 7 is evacuated by a vacuum pump connected via a trap 9, and the internal pressure is measured by a vacuum gauge 11.
- An appropriate mixed gas supply tube is connected to the quartz reaction tube 7, and a mixed gas of methane and hydrogen is fed into the quartz reaction tube 7 via this supply tube.
- the mixed gas for example, a mixture of 0.1 to 10% by volume, preferably 0.5 to 9% by volume, more preferably 1 to 8% by volume of hydrogen with hydrogen is suitable. is there. The evening is Decomposition results in TiC, and effective TiC coating cannot be obtained unless it reaches 0.1% by volume. On the other hand, if the mixing ratio exceeds 10% by volume, the hydrogen partial pressure is insufficient by that amount, and the adverse effect of oxygen and moisture contained in the atmosphere is likely to appear.
- the main gas concentration of the mixed gas is one of the factors controlling the amount of TiC supported.
- the electromagnetic wave oscillator 1 generates an electromagnetic wave having a frequency of 1 MHz to 10 GHz.
- electromagnetic waves this irradiates the Ti0 2 powder contained in the quartz reaction tube I, the powder particles are heated from the inside, the surface of the particles are activated.
- methane contained in the atmosphere inside the quartz reaction tube 7 is decomposed, and highly active carbon is generated. The carbon to form TiC and replaced with the lattice oxygen of the Ti0 2 powder particles.
- the photocatalyst of the present invention is capable of photodegrading inorganic substances, organic substances, bacteria, microorganisms and the like using light including visible light.
- the photocatalyst of the present invention can be used, for example, as a photocatalyst unit supported on a substrate.
- the substrate can be, for example, a plate-like article, a fiber, a particle, and can be transparent, translucent or opaque.
- the substrate can be selected from various materials and shapes depending on the use form of the photocatalyst.
- a unit in which a photocatalyst layer is formed on a substrate made of resin, metal, ceramics, or glass is For example, by attaching it to a window glass or a fluorescent lamp, it can function as a photocatalyst using sunlight or fluorescent light.
- the substrate is a wall material, a roof material, and a floor material, these members can be provided with a photocatalytic function.
- the formation of the photocatalyst layer on the substrate can be performed by coating the photocatalyst produced by the above method by a conventional method.
- a photocatalyst together with an appropriate solvent (eg, methanol or the like) and Z or a binder as necessary, and then heating and drying or heating (removing the binder and the solvent when using the binder and the solvent), the present invention Can be manufactured.
- an appropriate solvent eg, methanol or the like
- Z or a binder e.g., methanol or the like
- the present invention can be manufactured.
- forming a Ti0 2 layer onto the substrate at least a portion of the resulting Ti0 Ti0 2 layer of the substrate surface is treated with a plasma CVD method using a mixed gas such as the methane and hydrogen having a two-layer Ti
- a photocatalyst layer can be formed on the substrate.
- the reaction chamber 21 is provided with a substrate holder 24, a heater 22 for heating the substrate holder 24, and an RF electrode 26.
- a vacuum gauge 23 is provided in the reaction chamber 21, and a gas introduction system 30 for supplying a mixed gas, and two exhaust systems 28 and 2 for exhausting the inside of the reaction chamber 21. 9 is connected. Further, an RF power source 27 is connected to the RF electrode 26.
- the inside of the reaction chamber 21 is evacuated to a suitable degree of vacuum, then an appropriate mixed gas is introduced from the gas introduction system 30 and a voltage is applied from the RF power supply 27 to the substrate holder 24 and the RF electrode 26. Between them and plasma 25 is generated. The substrate on the substrate holder 24 is subjected to plasma processing by the plasma 25.
- the decomposed object By irradiating the photocatalyst or photocatalytic unit of the present invention with light containing at least visible light and bringing the decomposed object into contact with the photocatalyst or photocatalytic unit, the decomposed object can be decomposed.
- the light to be irradiated contains visible light. For example, there is no problem even if ultraviolet light is included in addition to visible light.
- the photocatalyst of the present invention exerts a photocatalytic action only with visible light.
- the heating temperature can be, for example, in the range of about 30 to 80 ° C.
- the photocatalyst and photocatalytic unit of the present invention are particularly suitable for oxidizing and decomposing organic compounds such as formaldehyde.
- the present invention includes a method for decomposing formaldehyde, which comprises contacting formaldehyde with a catalyst of the present invention or a catalyst layer of a photocatalytic unit using the photocatalyst of the present invention while irradiating light containing visible light.
- the light to be irradiated contains visible light. For example, it does not matter if it contains ultraviolet light in addition to visible light.
- the photocatalyst of the present invention exerts a photocatalytic action only with visible light.
- the catalytic function of photodecomposition of formaldehyde can be improved.
- the heating temperature is, for example, 3
- It can be in the range of about 0 to 80 ° C.
- the present invention includes an apparatus including the photocatalytic unit of the present invention.
- a device including a photocatalytic unit for example, a water purifying device, an air purifying device, a sterilizing device, a deodorizing device, a lighting device, a photocell, a water photolytic device, and the like can be opened.
- These apparatuses are known as apparatuses including a conventional photocatalytic unit, and the apparatus of the present invention can be configured by using the photocatalytic unit of the present invention in these known apparatuses.
- Figure 3 shows the binding energy spectra obtained by X-ray photoelectron spectroscopy (XPS) of the plasma-treated sample and the untreated sample.
- the X-ray photoelectron spectrometer used was an ULVAC-Fye Model558up (X-ray light source MgKa, incident angle 30 °).
- X-ray photoelectron spectrometer used was an ULVAC-Fye Model558up (X-ray light source MgKa, incident angle 30 °).
- titanium carbide is formed on the titania surface in addition to titania by the plasma treatment It was confirmed that it was.
- the peak height at 458.5 eV which is the binding energy of Ti2p3 / 2 in the above-mentioned spectrum, is 100
- the peak height of 4.55 eV attributed to TiC is 25 Is shown.
- Plasma-treated samples and untreated samples, further hydrogen reduction treatment were spectrum obtained by Raman spectroscopy of a sample for reference is shown in FIG.
- the Raman spectrometer used was a Perkin-Elma 12000 NIR-FT Raman system.
- the Raman absorption attributed to 0 to 1000 cnT Rico Ti-0 stretching and O-Ti-0 bending vibration was observed, while the hydrogen-reduced sample and the plasma treatment In the sample obtained, the absorption was significantly reduced.
- the Raman absorption attributed to Ti-0 stretching and 0-Ti-0 bending vibration at 0 to 1000 cm- 1 is stable over time for plasma-treated samples (changes even after storage in air for 6 months). None), whereas the hydrogen-reduced sample tends to change rapidly over time and return to the original peak, leaving about 50% of the untreated sample when left in air for 1 day. Returned. Raman absorption was observed at 3000 to 3500 cm- 1 in the sample treated with plasma, whereas the absorption was not observed in the sample treated with hydrogen.
- Anatase-type titania powder was subjected to plasma treatment in the same manner as in Example 1 except that the electromagnetic waves were changed to 200 W (Example 2), 300 W (Example 3), and 500 W (Example 4). Thus, a powder having only a gray surface was obtained.
- Example 1 to 4 The powders obtained in Examples 1 to 4 were subjected to DTA-TGA analysis. Exothermicity in the region over 700 ° C by differential thermal analysis (DTA) was slightly observed in the sample of Example 2, and the sample unit was changed in the order of Example 3, Example 1, and Example 4. The exothermic peak per weight continued to grow. In addition, the weight increase at a temperature exceeding 500 ° C by thermogravimetric analysis (TGA) was very small in the sample of Example 2, and the samples in Example 3, Example 1, and Example 4 An increase in weight gain per unit weight was observed.
- DTA differential thermal analysis
- TGA thermogravimetric analysis
- Example 1 The photocatalyst obtained in Example 1 was made into a paste with methanol, and an amount equivalent to 0.2 g of the photocatalyst of this paste was uniformly applied to a 60 ⁇ 60 mm glass substrate, and the paste was placed in an electric furnace at 300 ° C. For 1 hour (atmosphere: air) to obtain a photocatalytic unit of the present invention.
- Example 6 Vehicle light decomposition test of formaldehyde
- Example 5 Using a glass bell jar type reactor (1.9 liter), the inside of the system was diffused by a fan, and the substrate temperature of the photocatalytic unit prepared in Example 5 was adjusted by a heater. o ° c — fixed.
- the light source used was a halogen lamp (Nerohalo Cool Mini Soft, manufactured by Toshiba Lighting & Technology Corporation) that cuts ultraviolet light, and the wavelength passed through a glass filter (IRA-25S, manufactured by Toshiba Lighting & Technology Corporation) that cuts heat rays. Light in the range of 400 to 80 O nm was irradiated.
- FIG. 5 shows the relationship between light irradiation time and formaldehyde concentration. In the figure, indicates the result of this example, and it can be seen that the formaldehyde concentration decreased with the passage of light irradiation, and that formaldehyde was decomposed by the action of the photocatalyst of the present invention.
- the image shows the result when the glass plate used as the substrate was irradiated with light in the same manner as described above.
- the titanium oxide used as a raw material is applied to a glass plate as it is (without plasma treatment) in the same manner as in Example 5, and baked in an electric furnace at 300 ° C. for 1 hour (atmosphere: air).
- the formaldehyde concentration did not decrease with the passage of the light irradiation, indicating that the decomposition of formaldehyde did not proceed.
- Example 7 (Preparation of photocatalyst unit and decomposition test of formaldehyde with visible light) 0.2 g of the photocatalyst obtained in Examples 2 to 4 was uniformly applied to a 60 ⁇ 60 mm glass substrate, and placed in an electric furnace. The mixture was fired at 300 for 1 hour (atmosphere: air) to obtain a photocatalyst unit of the present invention. Using this photocatalytic unit, a formaldehyde decomposition test was performed in the same manner as in Example 6. As a result, the same results as in Example 6 were obtained, although the formaldehyde rate was different.
- the tar generated by burning the tobacco was dissolved in water to prepare a substance to be decomposed.
- the titanium oxide used as a raw material was applied to a glass plate as it was (without plasma treatment) in the same manner as in Example 5, and fired in an electric furnace at 300 for 1 hour (atmosphere: air).
- the activated solution was coated with 1 ml of an aqueous tar solution in the same manner as described above, and then irradiated with light.
- the brown color did not change even after 1 hour from the start of light irradiation, and almost no decomposition was progressed.
- 0.2 g of the photocatalyst obtained in Examples 2 and 3 was uniformly applied to a 60 ⁇ 60 mm glass substrate, and baked (atmosphere: air) at 300 ° C. for 1 hour in an electric furnace.
- the photocatalytic unit of the invention was obtained.
- a tar decomposition test was conducted in the same manner as in Example 6 using this photocatalyst unit. As a result, tar decomposition of the photocatalytic unit using the photocatalyst of Example 3 was the fastest.
- a 20-80 mesh anatase-type titania powder 2 g similar to that used in Example 1 was pasted with ethanol, and an amount equivalent to 0.2 g of titania of this paste was 60 ⁇ 60 mm glass substrate. Then, it was baked (atmosphere: air) in an electric furnace at 300 ° C for 1 hour as a pretreatment.
- the reactor was set in a substrate holder in a reaction chamber of a high-frequency (RF) plasma CVD apparatus of the parallel plate discharge type shown in FIG.
- Hydrogen containing 1% methane was supplied into the reaction chamber at a flow rate of 30 m 1 / min so that the substrate distance was 2 cm, the substrate processing temperature was 300 ° C., and the gas pressure was 0.1 Torr.
- Three types of samples were prepared with treatment times of 60 minutes, 90 minutes, and 120 minutes.
- the resulting photocatalytic unit is It had a dark brown color, and the binding energy spectrum and Raman spectrum obtained by the same X-ray photoelectron spectroscopy (XPS) as in Examples 1 to 4 were observed.
- XPS X-ray photoelectron spectroscopy
- Example 10 Using a glass bell jar type reactor (1.9 liter), the inside of the system was diffused with a fan, and the substrate temperature of the photocatalytic unit produced in Example 10 was kept at 30 ° C by a heater. did.
- An incandescent lamp with a central wavelength of 640 nm was used as the light source, and light including visible light was irradiated through a glass filter (IRA-25S, manufactured by Toshiba Lighting & Technology Corp.) that excites heat rays.
- acetate aldehyde was injected into the reactor to obtain a reaction gas having a predetermined concentration (100 ppm). After the acetoaldehyde reached the adsorption equilibrium, light irradiation was started. The reaction gas was analyzed by gas chromatography (FID) after passing through a methanizer.
- Figure 6 shows the relationship between light irradiation time and formaldehyde concentration.
- ⁇ plasma processing time: 60 minutes
- ⁇ plasma processing time: 90 minutes
- Kuni plasma processing time: 120 minutes
- the plot shows the blank results when the glass plate used as the substrate was irradiated with light in the same manner as above.
- the titanium oxide used as a raw material is applied to a glass plate as it is (without plasma treatment) in the same manner as in Example 10 and baked in an electric furnace at 300 ° C. for 1 hour (atmosphere: air)
- the concentration of acetoaldehyde hardly decreased with the lapse of time of light irradiation, indicating that the decomposition of acetoaldehyde did not substantially proceed.
- the reason why the concentration of acetate aldehyde is slightly reduced by the blank is that the acetate aldehyde is adsorbed on the inner wall of the reactor.
- a photocatalytic unit was prepared in the same manner as in Example 10 except that hydrogen containing 1% monomer was replaced with hydrogen containing no monomer or hydrogen containing 10% methane, and the treatment time was changed to 60 minutes. Produced.
- the photocatalyst unit obtained in place of hydrogen containing 10% methane exhibited a dark brown color, while the photocatalytic unit produced using hydrogen containing no methane exhibited a black color.
- Example 13 acetaldehyde Decomposition test using visible light
- the results are blank when the glass plate used for the substrate is irradiated with light in the same manner as above.
- the titanium oxide used as a raw material is applied to a glass plate as it is (without plasma treatment) in the same manner as in Example 10 and baked in an electric furnace at 300 ° C. for 1 hour (atmosphere: air)
- ⁇ I the result when hydrogen without methane is used.
- the concentration of acetoaldehyde hardly decreased with the lapse of time of light irradiation, indicating that the decomposition of acetoaldehyde did not substantially proceed.
- a new photocatalyst that can also use visible light.
- a photocatalyst capable of decomposing organic substances such as formaldehyde, acetoaldehyde, and tar
- a photocatalyst using such a photocatalyst It is also possible to provide a method for decomposing organic substances such as formaldehyde, acetate aldehyde, and tar.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU49671/97A AU4967197A (en) | 1996-11-25 | 1997-11-18 | Photocatalyst having visible light activity and uses thereof |
EP97912492A EP0997191A1 (en) | 1996-11-25 | 1997-11-18 | Photocatalyst having visible light activity and uses thereof |
US09/308,780 US6306343B1 (en) | 1996-11-25 | 1997-11-18 | Photocatalyst having visible light activity and uses thereof |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8/313598 | 1996-11-25 | ||
JP31359896 | 1996-11-25 | ||
JP3630097 | 1997-02-20 | ||
JP9/36300 | 1997-02-20 | ||
JP14953897 | 1997-06-06 | ||
JP9/149538 | 1997-06-06 |
Publications (1)
Publication Number | Publication Date |
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WO1998023374A1 true WO1998023374A1 (fr) | 1998-06-04 |
Family
ID=27289043
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1997/004191 WO1998023374A1 (fr) | 1996-11-25 | 1997-11-18 | Photocatalyseur ayant une activite lumineuse visible et utilisation de ce dernier |
Country Status (5)
Country | Link |
---|---|
US (1) | US6306343B1 (ja) |
EP (1) | EP0997191A1 (ja) |
CN (1) | CN1244818A (ja) |
AU (1) | AU4967197A (ja) |
WO (1) | WO1998023374A1 (ja) |
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JP2006239483A (ja) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | 資器材 |
JP4692987B2 (ja) * | 2005-02-28 | 2011-06-01 | 財団法人電力中央研究所 | 防腐装置 |
WO2007010665A1 (ja) * | 2005-07-21 | 2007-01-25 | Sarutashiki Nousan Limited Company | 高分散性二酸化チタン粉末 |
JP2010047475A (ja) * | 2009-11-24 | 2010-03-04 | Central Res Inst Of Electric Power Ind | 多機能性皮膜を有するガラス製品及びその製造方法 |
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AU4967197A (en) | 1998-06-22 |
EP0997191A4 (en) | 2000-05-03 |
EP0997191A1 (en) | 2000-05-03 |
US6306343B1 (en) | 2001-10-23 |
CN1244818A (zh) | 2000-02-16 |
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