CN1144614C - Porous photocatalysis and production thereof - Google Patents
Porous photocatalysis and production thereof Download PDFInfo
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- CN1144614C CN1144614C CNB011438258A CN01143825A CN1144614C CN 1144614 C CN1144614 C CN 1144614C CN B011438258 A CNB011438258 A CN B011438258A CN 01143825 A CN01143825 A CN 01143825A CN 1144614 C CN1144614 C CN 1144614C
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- China
- Prior art keywords
- porous
- photocatalysis
- titanium oxide
- hydrogel
- silica gel
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 title claims description 36
- 238000007146 photocatalysis Methods 0.000 title claims description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 claims abstract description 23
- 239000000017 hydrogel Substances 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000010408 film Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000002186 photoactivation Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 239000000741 silica gel Substances 0.000 description 28
- 229910002027 silica gel Inorganic materials 0.000 description 28
- 229960001866 silicon dioxide Drugs 0.000 description 28
- 239000003054 catalyst Substances 0.000 description 8
- 238000013459 approach Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 210000002706 plastid Anatomy 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- -1 titanium dioxide alkoxide Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a porous photocatalyst which not generating a crack in a porous photocatalyst manufacturing process, having excellent production efficiency and economical efficiency and rich in safety, weatherability, stability and workability, and a method for manufacturing the same. The porous photocatalyst uses a hydrogel with a water content of 30-80% is used as a starting raw material and a porous titanium oxide membrane is applied to the porous surface.
Description
Technical field
The present invention relates to porous photocatalysis and manufacture method thereof, this photochemical catalyst can be used as surrounding purifying material, is used for removing various stenches and the floating harmful substance of air, perhaps is used for wastewater treatment and clean water treatment.
Background technology
In recent years, have antibiotic, purification of water quality, deodorizing deodorization, pernicious gas are got rid of, the photochemical catalyst Products Development of usefulness such as air cleaning is very in vogue.The product of wherein representational use titanium oxide increases severely.Illustrational words, this series products mainly is used to construction material, outer wall material, window paper, purified water treatment device, places such as coating.Te Kaiping 7-303835 communique has been put down in writing titania photocatalyst and the manufacture method thereof with good photocatalysis performance, it is inner and/or its surperficial titania photocatalyst that contains iron compound of Titanium particles, use this photochemical catalyst, can be rapidly and remove the material that human body and living environment is had dysgenic material and has this possibility as organic halogen compound, foul gas, oil, bacterium, mushroom, algae etc. effectively.
Put down in writing in the Te Kaiping 6-298520 communique method that titania photocatalyst applies has been carried out on the silica gel surface, that is to say it is to make the method for silica gel that contains the ultramicron of titanium oxide with dispersity, employing is distributed to the ultramicron of titanium oxide after the silicon oxide colloid, colloidal gelization, sintering then, utilize this method, carry out simple operations, can obtain to have sealing quantum effect and the good titanium oxide ultra micron dispersion silica gel of transparency effectively with the raw material that buys easily.
Do not have economy and high efficiency but above technology is talkative.For example, directly apply the occasion of photochemical catalyst on silica gel surface,,, cause silica gel to be broken into fragment by heating owing to rapid moisture absorption causes the expansion of silica gel and the heating that absorption causes in the silica gel immersion photocatalyst sol during dip-coating.Thus, can not obtain the commodity of expection.The result can only screen the silica gel that breaks, intact silica gel as commodity.In order to reduce breakage rate as far as possible, allow silica gel absorb water vapour at leisure, or be immersed in the liquid, or method such as infiltration.But these class methods still have the possibility that absorbs water vapour again in the operational phase that the silica gel commodity are handled again, are difficult to the control moisture content.In addition, in the method for the vaporific photocatalyst sol of silica gel surface spraying, or silica gel is placed under the high humility method such as long-time exposure, but these all are the methods of ignoring operability and economy.
Summary of the invention
Porous photocatalysis involved in the present invention and manufacture method thereof are the defectives in view of above-mentioned technology, develop through studying intensively meticulously.The purpose of this invention is: a kind of porous photocatalysis and manufacture method thereof are provided, in the manufacturing pilot process of silica gel, make made hydrogel spherical in shape and keep the performance of photochemical catalyst, provide economical and practically surrounding purifying material with good security, stability, operability-.
Synthetic photochemical catalyst porous plastid has two kinds of methods.A kind of is to make the titanium oxide grain, and another kind is to carry out the photocatalysis thinner on the surface of porous raw materials such as silica gel.But these two kinds of methods are all infeasible in view of production efficiency or economic angle.Silica gel surface light catalysis thinner method is both economical, but production efficiency is low.In order to overcome the above problems, present inventors have obtained this achievement in research finally through studying intensively meticulously and the improvement of technology having been carried out inquiring into repeatedly.
The present invention is: porous photocatalysis, it is characterized in that with the hydrogel being initiation material, and cover porous matter surface on the surface with thin film of titanium oxide; Porous photocatalysis is characterized in that the initiation material that uses is the hydrosol of moisture content 30%～80%; Porous photocatalysis is characterized in that, on the titanium oxide porous film pore is arranged, and the pore aperture is adjusted to any number in 1nm～10 mu m ranges during fabrication; Porous photocatalysis, the crystal formation that it is characterized in that the titanium oxide porous film is a Detitanium-ore-type; The manufacture method of porous photocatalysis is characterized in that, is initiation material with the hydrogel, puts it in the photocatalyst sol and soaks, and perhaps photoactivation agent colloidal sol is sprayed on hydrogel surface coated with titanium oxide film, and is dried; The manufacture method of porous photocatalysis, the moisture content that it is characterized in that hydrogel is 30%～80%.
The specific embodiment
The present invention adopts the production method different with silica gel synthesis procedure in the past to come the synthesis material hydrogel.Even and this hydrogel directly is immersed in the photocatalyst solution and also can keeps shape, can not resemble and break the silica gel.Production efficiency also improves a lot than the synthetic method of silica gel in the past for this reason.Hydrogel used in the present invention with allowed the moisture method of silica gel different in the past, obtain after the moisture modulation of silica gel being carried out height and the classification.Among the present invention employed photocatalyst sol is had no particular limits.For example, can be from titanium dioxide alkoxide, halogenated titanium, or the Titanium modulation forms.Perhaps can from commercially available known products such as photocatalyst sol, select use arbitrarily.
Embodiment
Representational embodiment of the present invention is as follows.
Embodiment 1 (modulator approach of hydrogel)
After 100 weight portion sulfuric acid (20 weight %) and two kinds of solution of 100 weight portion sodium metasilicate (24 Baume degrees) are mixed, react, wash with water, obtain hydrogel.Hydrogel is carried out drying, the moisture adjustment, classification is handled.At this time allow the moisture content of hydrogel preferably remain between 30%～80%.Special in about 60%, be to have production efficiency and most economical most.
Embodiment 2 (modulator approach of photocatalyst sol)
Of the absolute ethyl alcohol dilution of 60 gram titanium tetraisopropylates with 500 milliliters.Add 20 gram diethanol amine and 5 gram water while stirring.And then add the polyethylene glycol of 5 gram-molecular weights 1000, be deployed into transparent sol solutions.
Embodiment 3 (modulator approach 1 of porous photocatalysis)
The hydrogel that embodiment 1 is synthesized is put into the photocatalyst sol immersion taking-up afterwards in 5 minutes that embodiment 2 is allocated, fully remove photocatalyst sol, dry down at 170 ℃.Be warming up to 500 ℃ of sintering then, make the crystal formation of titanium dioxide be converted into Detitanium-ore-type, thereby obtain porous photocatalysis from rutile-type.
Embodiment 4 (modulator approach 2 of porous photocatalysis)
The photocatalyst sol AT-01 solution that the hydrogel that embodiment 1 is synthesized is put into Photo Catalytic Materials Inc.'s system soaks and takes out after 5 minutes, fully removes photocatalyst sol, and is dry down at 170 ℃.AT-01 has been converted into Detitanium-ore-type because of this photocatalyst sol, so can obtain porous photocatalysis after the drying.
Embodiment 5 (modulator approach of porous photocatalysis 3)
Modulation porous photocatalysis sol solutions similarly to Example 2 is with spraying process coated with titanium oxide film.Promptly hydrogel is placed on the tiny wire netting of mesh, sprays while rock with colloidal sol.After dry room temperature is adjusted to 170 ℃ of preheatings, heats again, just can make porous photocatalysis to 500 ℃ of sintering.This is operated repeatedly after the several, and the thickness of film and photolytic activity increase.
Embodiment 6 (modulator approach 4 of porous photocatalysis)
Use AT-01 photocatalyst sol (Photo Catalytic Materials Inc.'s system), use the method identical to spray A type spherical silica-gel (JIS standard items) with embodiment 5.At leisure temperature is warmed to 170 ℃ from room temperature and comes drying, make porous photocatalysis thus.
Embodiment 7 (photochemical catalyst Evaluation on effect method)
Being placed on respectively in the aqueous solution of methylene blue that contains 100ppm through embodiment 3,4,5,6 obtained porous photocatalysis, after black light lamp irradiation 24 hours, the methylenum careuleum of observing the porous photocatalysis surface has all disappeared.To not carrying out finding that methylenum careuleum does not disappear after the same operation through the silica gel of photocatalyst coating.Obviously, embodiment 3,4, and 5,6 silica gel that synthesized are porous photocatalysis.
Comparative example 1
When A type spherical silica-gel (JIS standard items) is put into AT-01 photocatalyst sol (Photo Catalytic Materials Inc.'s system) dip-coating, exothermic reaction is arranged at once, be accompanied by the sound that breaks and see that silica gel is broken into small particle.
Comparative example 2
After using AT-01 photocatalyst sol (Photo Catalytic Materials Inc.'s system) spraying A type spherical silica-gel (JIS standard items), there is minute crack to occur on the surface of silicon particle.
[overall merit]
| Silica gel raw material moisture content (%) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| The breakage that has or not dip-coating to cause | × | × | × | ○ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ |
| The effect of photochemical catalyst | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ◎ | ○ | × |
| Commodity value | × | × | × | ○ | ◎ | ◎ | ◎ | ◎ | ○ | × |
Annotate: * expression is poor, and zero expression is general, and ◎ represents well.
According to the present invention, porous photocatalysis can not break and the crack in manufacture process.
Adopt words of the present invention to have porous photocatalysis can be provided expeditiously economically.And this porous photocatalysis has very good security, weatherability, stability, operability.
Claims (4)
1. porous photocatalysis is characterized in that, to be initiation material by sulfuric acid and sodium metasilicate reaction hydrogel that obtain, moisture content 30～80%, covers porous matter surface on the surface with thin film of titanium oxide.
2. the porous photocatalysis of claim 1 record has pore on the thin film of titanium oxide that it is characterized in that covering, and the pore aperture is modulated onto any number in 1nm～10 mu m ranges during fabrication.
Claim 1 or 2 the record porous photocatalysis, the crystal formation that it is characterized in that the titanium oxide porous film is a Detitanium-ore-type.
4. the manufacture method of porous photocatalysis, it is characterized in that to react hydrogel that obtain, moisture content 30～80% by sulfuric acid and sodium metasilicate be initiation material, it is put into photocatalyst sol flood, perhaps the spraying of photoactivation agent colloidal sol is dried then with the coated with titanium oxide film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000388108A JP3992129B2 (en) | 2000-12-21 | 2000-12-21 | Method for producing porous photocatalyst |
| JP388108/2000 | 2000-12-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1363421A CN1363421A (en) | 2002-08-14 |
| CN1144614C true CN1144614C (en) | 2004-04-07 |
Family
ID=18854904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011438258A Expired - Fee Related CN1144614C (en) | 2000-12-21 | 2001-12-14 | Porous photocatalysis and production thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3992129B2 (en) |
| CN (1) | CN1144614C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010151563A1 (en) * | 2009-06-25 | 2010-12-29 | 3M Innovative Properties Company | Light-activated antimicrobial article and method of use |
| CN102284073B (en) * | 2010-06-18 | 2014-09-24 | 北京纳琦环保科技有限公司 | Nano-photocatalyst exhaust fan |
| KR101465299B1 (en) * | 2012-05-25 | 2014-12-04 | (주)엘지하우시스 | Photocatalyst, method for preparing the same and photocatalyst device |
| KR101450389B1 (en) * | 2012-05-25 | 2014-10-14 | (주)엘지하우시스 | Photocatalyst, method for preparing the same and photocatalyst device |
| CN103730259B (en) * | 2013-12-27 | 2016-08-17 | 沈阳工业大学 | A kind of nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film and preparation method thereof |
| KR101824181B1 (en) | 2016-04-06 | 2018-01-31 | 가천대학교 산학협력단 | Manufacturing method of recyclable photocatalyst and photocatalyst made by the same |
-
2000
- 2000-12-21 JP JP2000388108A patent/JP3992129B2/en not_active Expired - Lifetime
-
2001
- 2001-12-14 CN CNB011438258A patent/CN1144614C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3992129B2 (en) | 2007-10-17 |
| JP2002186861A (en) | 2002-07-02 |
| CN1363421A (en) | 2002-08-14 |
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Granted publication date: 20040407 Termination date: 20101214 |