CN1197662C - Method for forming metal composite titanium dioxide nano particle film on ceramic surface - Google Patents
Method for forming metal composite titanium dioxide nano particle film on ceramic surface Download PDFInfo
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- CN1197662C CN1197662C CN 01131336 CN01131336A CN1197662C CN 1197662 C CN1197662 C CN 1197662C CN 01131336 CN01131336 CN 01131336 CN 01131336 A CN01131336 A CN 01131336A CN 1197662 C CN1197662 C CN 1197662C
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 62
- 239000000919 ceramic Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 41
- 239000002905 metal composite material Substances 0.000 title claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000746 purification Methods 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 17
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 22
- -1 polyoxyethylene Polymers 0.000 claims description 22
- 239000006228 supernatant Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000013049 sediment Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 2
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims 1
- 238000005507 spraying Methods 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000001782 photodegradation Methods 0.000 abstract 1
- 229960005196 titanium dioxide Drugs 0.000 description 50
- 235000010215 titanium dioxide Nutrition 0.000 description 50
- 238000002360 preparation method Methods 0.000 description 24
- 239000012528 membrane Substances 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001332 colony forming effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a method for forming a metal composite titanium dioxide nano particle film on a ceramic surface. (1) Under stirring, adding deionized water and/or a surfactant into 20-100 parts of the metal composite titanium dioxide nano particle sol, and uniformly stirring; (2) spraying the sol obtained in the step (1) on the surface of the ceramic, drying in the air, and drying at 50-300 ℃ for 10 minutes-5 hours; or spraying the sol obtained in the step (1) on the surface of the bisque-fired ceramic, and drying in the air; (3) and (3) keeping the temperature of the ceramic product coated with the metal composite titanium dioxide nano particle film at 300-1300 ℃ for 10 minutes-10 hours. The metal composite titanium dioxide nano particle film with the light purification function formed on the surface of the ceramic shows good photodegradation efficiency, and also shows good antibacterial efficiency under indoor natural light or lower ultraviolet light intensity.
Description
Technical field
The invention belongs to technical field of nano material, particularly on ceramic surface, form a series of methods with metal composite titanium dioxide nano particle film of sterilization, mildew-resistant, deodorizing, degradable organic pollutant, resolving harmful gas ability with light purification function.
Background technology
At present, utilize titanium dioxide optical catalyst to carry out environmental purification and caused widely and to pay attention to, aspect the raising of the preparation of titanium dioxide optical catalyst, photocatalytic activity, photocatalyst fixing, also carried out number of research projects.The report of this respect can be referring to " chemical material " 1996 the 8th volumes the 2180th page of (Vinodgopal, K.; Bedja, I., Kamat, P.V., Chem.Mater., 1996,8,2180) and " physical chemistry magazine " 1994 the 98th volumes 13669 pages (Choi, W., Termin, A., Hoffmann, M.R., J.Phys.Chem., 1994,98,13669) etc.Titanium dioxide optical catalyst is supported in certain substrate, can overcomes separation difficulty, easily cohesion waits powder photocatalyst not fit into the shortcoming of flow circuit system, and simultaneously, the substrate that is fixed with photocatalyst has also had photo-catalysis function.The method of stagnant catalyst commonly used has two kinds at present.A kind of is that the powder-type titanium deoxide catalyst that will prepare is fixed on certain carrier; Another kind method be alkoxide with titanium as precursor, by the stable TiO 2 sol of Prepared by Sol Gel Method, TiO 2 sol is supported in certain substrate prepares titanium dioxide nano particle film again, and then reach the purpose of stagnant catalyst.The report of this respect can be referring to " nature " 1997 the 388th volumes 431 pages of (Wang, R., Hashimoto, K., Fujishima, A., Nature, 1997,388,431), " new The Chemicals " 1996 20 volumes 233 pages of (Sitkiewiitz, S., Heller, A., New J.Chem., 1996,20,233) and 726 pages of (Sunada of " environmental science and technology " 1998 the 32nd volume, K., Kikuchi, Y., Hashimoto, K., Fujishima, A., Eviron.Sci.Techno., 1998,32,726) etc.But the titanium dioxide optical catalyst poor adhesive force often appears in preceding a kind of fixing means, caducous problem; The raw material that then a kind of method is used is generally the higher metal alkoxide of price, and cost is higher; Moreover the research of a kind of method in back mainly concentrates on titanium dioxide nano particle film at the fixing glass that has the light purification function in order to preparation on glass.But when ceramic surface prepares light purification function film, owing to the sintering temperature that fixed photocatalyst is required is higher, the technology of preparing when ceramic surface prepares light purification function film will be different with the technology of preparation light purification glass.Moreover when a kind of method in back prepared titanium dioxide nano particle film, used TiO 2 sol was made up of unbodied titanium dioxide nano-particle, after the film forming, anatase phase at first appears, along with the rising of sintering temperature in sintering process, the generation crystalline phase transforms, and becomes rutile phase.This crystalline phase in the sintering process transforms the cracking that causes film easily.
Summary of the invention
One of purpose of the present invention provides a kind of method that forms metal composite titanium dioxide nano particle film on ceramic surface, has the ceramic of antibiotic, mildew-resistant, degradation of contaminant function in order to preparation.
Another object of the present invention is that metal inorganic salt-titanium tetrachloride cheap more with relative metal alkoxide, that be easy to get is a main raw material, the utilization Hydrothermal Preparation has the metal composite titanium dioxide nano particle colloidal sol of certain crystal formation, as the raw material of realizing the inventive method, be used for overcoming the pottery shortcoming that crystal formation changes in sintering process with this colloidal sol.
The objective of the invention is to realize by following technical proposals:
(1) Hydrothermal Preparation metal composite titanium dioxide nano particle colloidal sol;
(2) behind the adjusting collosol concentration, the metal composite of preparation light purification function after ceramic surface is filmed
Titanium dioxide nano particle film.
The preparation method of metal composite titanium dioxide nano particle colloidal sol of the present invention is a raw material with the titanium tetrachloride, the utilization Hydrothermal Preparation.This method may further comprise the steps, and related amount is in parts by weight:
(1) gets 15～65 parts of titanium tetrachlorides and be dissolved in 35～85 portions of frozen water, stir, obtain transparent, clarifying titanium tetrachloride aqueous solution;
(2) under stirring fast, the adding transition metal salt is dissolved in 0.1～30 part of the solution that generates in 90～100 parts the deionized water in the titanium tetrachloride aqueous solution of 10～50 parts of steps (1), and this transition metal salt can be by the complexing agent complexing; Stir, add deionized water again, stir, press in the still constant temperature under 50～400 ℃ of temperature during above-mentioned solution is transferred to;
(3) naturally cooling, the supernatant liquid that inclines, centrifuge washing lower sediment; Collect the supernatant liquid that obtains in the centrifuge washing process, obtain metal composite titanium dioxide nano particle colloidal sol.
Described step (2) further added 30～85 parts of deionized waters before constant temperature.
Described step (2) constant temperature 0.5～7 hour.
Described salt is transition metal chloride or metal nitrate.As iron(ic) chloride, Silver Nitrate, cupric nitrate etc.
Described transition metal is iron, nickel, platinum, iridium, palladium, silver, zinc or copper etc.
Described complexing agent is ammoniacal liquor, oxalate, thiosulphate or thiocyanate-etc.
The metal composite titanium dioxide nano particle colloidal sol of the present invention's preparation mainly is made up of metal composite titanium dioxide nano particle and water.The weight percentage of metal composite titanium dioxide nano particle is 0.03～0.5%.。
The composition of metal composite titanium dioxide nano particle of the present invention and content are:
Metal ion 0.005～5 weight part
Titanium dioxide 95～100 weight parts
The particle diameter of described metal composite titanium dioxide nano particle is 3～50 nanometers, preferred 3～10 nanometers.
The metal composite titanium dioxide nano particle colloidal sol that the present invention is prepared, used water is regulated collosol concentration, colloidal sol is sprayed at the ceramic bodies surface, behind the air drying, pre-burning, repeat to film, can form metal composite titanium dioxide nano particle film at ceramic surface with suitable temperature sintering again with light purification function.
Form the method for metal composite titanium dioxide nano particle film on ceramic surface, this method may further comprise the steps, and related amount is in parts by weight:
(1) under agitation, in 20～100 parts of metal composite titanium dioxide nano particle colloidal sols, add 0～80 part deionized water and 0～10 part tensio-active agent, stir;
(2) colloidal sol with step (1) is sprayed at ceramic surface, and air drying is again in 50～300 ℃ of dryings 10 minutes～5 hours;
Or the colloidal sol of step (1) is sprayed at the ceramic surface of biscuiting, air drying;
(3), be 300～1300 ℃ of following constant temperature 10 minutes～10 hours in temperature with the above-mentioned ceramic that is covered with metal composite titanium dioxide nano particle film.
In order to guarantee the thickness of film on the ceramic, but repeating step is more than (2) 1 times.
Described tensio-active agent is polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, sodium laurylsulfonate or cetyl trimethylammonium bromide etc.
The particle diameter of described titanium dioxide nano-particle is 3～50 nanometers.
By the metal composite titanium dioxide nano particle film that the inventive method forms on ceramic surface, have antibiotic, mildew-resistant, deodorizing, decomposing pollutant function, and can improve the hydrophilicity of said products to a certain extent with light purification function.
The metal composite titanium dioxide nano particle film with light purification function by the inventive method forms on ceramic surface shows good the disposal efficiency, has also shown excellent antibiotic efficient under indoor natural light or lower ultraviolet ray intensity.
Advantage of the present invention and positively effect:
Adopt the method among the present invention to compare with general method, have the following advantages in the method that the ceramic surface preparation has the composite metal-TiO 2 particle membrane of light purification function:
1. raw materials used low price is easy to get:
Adopt the method among the present invention, when ceramic surface prepares light purification function film, during the preparation TiO 2 sol, be with titanium tetrachloride as main raw material(s), used starting material are that raw material is cheaply a lot of with the metal alkoxide with sol-gel method, and raw material is easy to get.
2. Zhi Bei TiO 2 sol is made up of the titanium dioxide nano-particle with certain crystal formation.
When method commonly used prepares light purification function film, employed TiO 2 sol, by Prepared by Sol Gel Method, TiO 2 sol mainly is made up of unbodied titanium dioxide nano-particle, in sintering process, crystallization can take place, and crystal formation transforms.These all make the film cracking easily.And in the present invention, use the Hydrothermal Preparation TiO 2 sol, gained colloidal sol is made up of the crystalline state TiO 2 particles, is not prone to above-mentioned phenomenon during sintering.
3. compare more stable with the TiO 2 sol that the sol-gel method of routine prepares:
The light purification function film of the present invention's preparation, its used metal composite titanium dioxide nano particle colloidal sol can at room temperature be placed the several months.
4. the preparation method is simple, easily row:
Adopt method of the present invention, method is simple when ceramic surface prepares light purification function film, easily row.Among the present invention during preparation light functional membrane, use be very simple spraying method, the glaze spraying technology in the similar Production of Ceramics of this method can drop into by minimizing equipment.
5. catalytic activity height:
The present invention shown in accompanying drawing 2,3,4, has very high photocatalytic activity at the light purification function film of ceramic surface preparation.
6. antimicrobial efficiency height:
As described in Example 7.Under the indoor natural light condition, the present invention has shown quite high antimicrobial efficiency fruit at the light purification function film of ceramic surface preparation; Under lower ultraviolet ray intensity, to compare with the titanium-dioxide photo purification membrane of general method preparation, antibacterial effect is also very remarkable.
Description of drawings
Fig. 1. the embodiment of the invention 6, at the stereoscan photograph of the light purification function film of ceramic surface preparation.
Fig. 2. the embodiment of the invention 4, at the light purification function film of ceramic surface preparation, photocatalytic degradation azoic dyestuff tropeolin-D, the absorption spectrum of remaining tropeolin-D is with the variation of light application time; From top to bottom, light application time is followed successively by 0,1,2,3,4 hours.
Fig. 3. the embodiment of the invention 5, at the light purification function film of ceramic surface preparation, photocatalytic degradation azoic dyestuff tropeolin-D, the absorption spectrum of remaining tropeolin-D is with the variation of light application time; From top to bottom, light application time is followed successively by 0,2,4,6 hours.
Fig. 4. the embodiment of the invention 8, at the light purification function film of ceramic surface preparation, photocatalytic degradation azoic dyestuff tropeolin-D, the absorption spectrum of remaining tropeolin-D is with the variation of light application time; From top to bottom, light application time is followed successively by 0,1,2,3,4,5 hours.
Embodiment
Embodiment 1
Get 22 weight part titanium tetrachlorides and be dissolved in the 78 weight part frozen water, stir, obtain transparent, clarifying titanium tetrachloride aqueous solution; Under stirring fast, the 1 part of iron trichloride that adds 20 weight parts in the above-mentioned titanium tetrachloride aqueous solution of 40 weight parts is dissolved in the solution that is generated in the deionized water of 99 weight parts, after continuing stirred for several minute, the deionized water that adds 40 parts again, stir, be transferred in the teflon-lined and press in the still, 150 ℃ of constant temperature 2 hours naturally cools to room temperature.The supernatant liquid that inclines, the deionized water wash lower sediment in the centrifuge washing process, is collected supernatant liquid, obtains iron ion compound titanium dioxide nano sol.
Get 30 parts of above-mentioned iron ion composite titanium dioxide Nano sols, under agitation, add 68 parts of water and 2 parts of polyglycol surfactants, after stirring, be sprayed on the finished product ceramic plate, after the drying at room temperature, 100 ℃ of dry half an hour, after repeating to be coated with membrane process 2 times, in the muffle furnace in 400 ℃ of constant temperature after 8 hours, naturally cooling.Obtain having the metal composite titanium dioxide nano particle film of light purification function at ceramic surface.
Embodiment 2
Get 60 weight part titanium tetrachlorides and be dissolved in the 40 weight part frozen water, stir, obtain transparent, clarifying titanium tetrachloride aqueous solution; Under stirring fast, the 1 part of cupric nitrate that adds 10 weight parts in the above-mentioned titanium tetrachloride aqueous solution of 14 weight parts is dissolved in the solution that is generated in the deionized water of 99 weight parts, after continuing stirred for several minute, the deionized water that adds 76 parts again, stir, transfer in the teflon-lined autoclave, 100 ℃ of constant temperature 2 hours naturally cools to room temperature.The supernatant liquid that inclines, the deionized water wash lower sediment.In the centrifuge washing precipitation process, collect supernatant liquid, obtain cupric ion compound TiO 2 sol.
Get 89 parts of above-mentioned cupric ion composite titanium dioxide Nano sol liquid, under agitation, deionized water and 1 part of polyvinyl alcohol tensio-active agent of adding 10 parts, after stirring, be sprayed on the finished product ceramic plate, after the drying at room temperature, 250 ℃ of dryings 1 hour, after repeating to be coated with membrane process 5 times, in the muffle furnace in 700 ℃ of constant temperature after 2 hours, naturally cooling.Obtain having the copper composite titanium dioxide nano particle film of light purification function at ceramic surface.
Embodiment 3
Get 22 weight part titanium tetrachlorides and be dissolved in the 78 weight part frozen water, stir, obtain titanium tetrachloride aqueous solution; Under vigorous stirring, the 1 part of Silver Nitrate that adds 5 weight parts in the above-mentioned titanium tetrachloride aqueous solution of 45 weight parts is dissolved in the solution that is generated in the deionized water of 99 weight parts, after continuing stirred for several minute, again to the deionized water that wherein adds 50 parts, stir, be transferred in the teflon-lined and press in the still, 250 ℃ of constant temperature 1 hour naturally cools to room temperature.The supernatant liquid that inclines, the centrifuge washing lower sediment is collected supernatant liquid in the washing process, obtain silver ions compound TiO 2 sol.
Get 50 parts of above-mentioned silver ions composite titanium dioxide Nano sol liquid, under agitation, add 50 parts of deionized waters, mix, be sprayed on the finished product ceramic plate, after the drying at room temperature, 250 ℃ of dryings 20 minutes, after repeating to be coated with membrane process 3 times, in the muffle furnace in 500 ℃ of constant temperature after 30 minutes, naturally cooling.Obtain light purification function film at ceramic surface.
Embodiment 4
Get 35 weight part titanium tetrachlorides and be dissolved in the 65 weight part frozen water, stir, obtain titanium tetrachloride aqueous solution; Under vigorous stirring, 5 parts of chloro-iridic acid ammonia that add 0.5 weight part in the above-mentioned titanium tetrachloride aqueous solution of 30 weight parts are dissolved in the solution that deionized water generated of 95 weight parts, after continuing stirred for several minute, to wherein adding 69.5 parts of deionized waters, after stirring, be transferred in the teflon-lined and press in the still, 180 ℃ of constant temperature 1 hour naturally cools to room temperature.Incline behind the supernatant liquid, the centrifuge washing lower sediment is collected the supernatant liquid in the centrifuge washing process, obtains iridium ion compound titanium dioxide nano sol.
Get 75 parts of above-mentioned iridium ion composite titanium dioxide colloidal sols, after adding 24.95 parts of deionized waters and 0.05 part of polyoxyethylene glycol, mix, be sprayed on the finished product ceramic plate, after the drying at room temperature, 180 ℃ of dryings 10 minutes are after repeating to be coated with membrane process 5 times, in the muffle furnace in 600 ℃ of constant temperature after 5 hours, naturally cooling.Obtain the iridium ion compound titanium dioxide film of light purification function at ceramic surface.
Get 50 weight part titanium tetrachlorides and be dissolved in the 50 weight part frozen water, stir, obtain transparent, clarifying titanium tetrachloride aqueous solution; Under stirring fast, 5 parts of amminos that add 19 weight parts in the above-mentioned titanium tetrachloride aqueous solution of 20 weight parts close Silver Nitrate and are dissolved in the solution that is generated in the deionized water of 95 weight parts, after continuing stirred for several minute, the deionized water that adds 61 parts again, after stirring, be transferred in the teflon-lined and press in the still, 120 ℃ of constant temperature 3 hours naturally cools to room temperature.The supernatant liquid that inclines, the centrifuge washing lower sediment is collected the supernatant liquid in the centrifuge washing process, obtains silver ions compound TiO 2 sol.
Get 50 parts of above-mentioned silver ions composite titanium dioxide Nano sol liquid, under agitation, add 50 parts of water, after mixing, be sprayed on the finished product ceramic plate, after the drying at room temperature, 180 ℃ of dryings 1.5 hours, after repeating to be coated with membrane process 2 times, in the muffle furnace in 800 ℃ of constant temperature after 3 hours, naturally cooling.On porcelain facing, obtain light purification function silver ions dioxide composite titanium film.
Embodiment 6
Get 22 weight part titanium tetrachlorides and be dissolved in the 78 weight part frozen water, stir, obtain titanium tetrachloride aqueous solution; Under vigorous stirring, 8 parts of amminos that add 25 weight parts in the above-mentioned titanium tetrachloride aqueous solution of 40 weight parts close cupric nitrate and are dissolved in the solution that is generated in the deionized water of 92 weight parts, after continuing stirred for several minute, add 35 parts of deionized waters, after stirring, be transferred in the teflon-lined and press in the still, 350 ℃ of constant temperature 5 hours naturally cools to room temperature.The supernatant liquid that inclines, the centrifuge washing lower sediment.In the centrifuge washing process, collect supernatant liquid, obtain cupric ion compound titanium dioxide nano sol.
Get 40 parts of above-mentioned cupric ion composite titanium dioxide Nano sols, under agitation, add 55 parts of water and 5 parts of sodium laurylsulfonates, be sprayed on the finished product ceramic plate, after the drying at room temperature, 150 ℃ of pre-burnings 3 hours, after repeating to be coated with membrane process 5 times, in the muffle furnace in 550 ℃ of constant temperature after 3 hours, naturally cooling.Obtain having sterilization, the ceramic product of degradation of contaminant function.
Embodiment 7
Get 35 weight part titanium tetrachlorides and be dissolved in the 65 weight part frozen water, stir, obtain titanium tetrachloride aqueous solution; Under vigorous stirring, the 1 part of ammino that adds 3 weight parts in the above-mentioned titanium tetrachloride aqueous solution of 23 weight parts closes Silver Nitrate and is dissolved in the solution that generates in the deionized water of 99 weight parts, after continuing stirred for several minute, add 74 parts of deionized waters again, after stirring, be transferred in the teflon-lined and press in the still, 250 ℃ of constant temperature 0.5 hour naturally cools to room temperature.The supernatant liquid that inclines, the centrifuge washing precipitation.In the process of centrifuge washing, collect supernatant liquid and can obtain silver ions compound TiO 2 sol.
Get 50 parts of above-mentioned silver ions composite titanium dioxide Nano sols, to wherein adding 50 parts of water, be sprayed on the finished product ceramic plate under stirring, after the drying at room temperature, 150 ℃ of pre-burning half an hour are after repeating to be coated with membrane process 3 times, in the muffle furnace in 450 ℃ of constant temperature after 3 hours, naturally cooling.
The antibacterial effect of the self-cleaning ceramic sheet of preparation under indoor natural light and very low ultraviolet ray intensity in the embodiment of the invention 7.
| Sample | The bacterium original concentration | Ultraviolet lighting intensity | Light application time/hour | The killing bacteria ratio |
| Data in literature 1 | 30 000 | 1.0mW/cm 2 | 1 | Almost kill all bacteriums |
| Data in literature 2 | 200 000 | 0.4mW/cm 2 | 1 | ＜25％ |
| Experimental group 1 | 80 000 | Unglazed photograph | ＞51％ | |
| Experimental group 2 | 80 000 | 0.04mW/cm 2 | 1 | ＞62％ |
Experimental group 1 and 2 (this project sample)
Bacterial concentration: primitive bacteria number=4.2 * 10
5Individual=0.2mL * 4.2 * 10
5CFU (colony-forming unit)
Usable floor area: area=3.14cm
2(diameter=2cm)
Document 1 data are from " photochemistry and photo bio magazine " 1997 the 106th volumes the 52nd page of (Kikuchi, Y., Sunada, K., Iyoda, T., Hashimoto, K., Fujishima, A., J.Photochem.﹠amp; Photobio.A:Chem., 1997,106,52) (Japan)
Primitive bacteria number=30 000=0.15mL * 2 * 10
5CFU/mL
Usable floor area: 1.57cm
2(diameter=1cm)
Document 2 data are from 726 pages (Sunada, K., Kikuchi, Y., Hashimoto, K., Fujishima, A., 1998,32,726) (Japan) of " environmental science and technology " 1998 the 32nd volumes
Primitive bacteria number=200 000=1ml * 2 * 10
5CFU/ml
Embodiment 8
Get 22 weight part titanium tetrachlorides and be dissolved in the 78 weight part frozen water, stir, obtain titanium tetrachloride aqueous solution; Under vigorous stirring, the 0.2 part of iron trichloride that adds 0.5 weight part in the above-mentioned titanium tetrachloride aqueous solution of 45 weight parts is dissolved in the solution that is generated in the deionized water of 99.8 weight parts, after continuing stirred for several minute, after adding 54.5 parts deionized water again, stir, be transferred in the teflon-lined and press in the still, 150 ℃ of constant temperature 2 hours naturally cools to room temperature.The supernatant liquid that inclines, the deionized water wash lower sediment.In the centrifuge washing process, collect supernatant liquid, obtain iron ion compound titanium dioxide nano sol.
Get 70 parts of above-mentioned iron ion composite titanium dioxide Nano sols, under agitation, add 30 parts of deionized waters, after stirring, be sprayed on the ceramic plane of biscuiting, in the muffle furnace in 1255 ℃ of constant temperature after 15 minutes, naturally cooling.Obtain having the film of light purification function at ceramic surface.
Embodiment 9
Get 22 weight part titanium tetrachlorides and be dissolved in the 78 weight part frozen water, stir, obtain titanium tetrachloride aqueous solution; Under vigorous stirring, the Silver Nitrate that adds 3 parts of potassium sulfocyanate complexings of 1 weight part in the above-mentioned titanium tetrachloride aqueous solution of 50 weight parts is dissolved in the solution that is generated in the deionized water of 97 weight parts, after continuing stirred for several minute, the deionized water that adds 49 parts again, after stirring, be transferred in the teflon-lined and press in the still, 120 ℃ of constant temperature 6 hours naturally cools to room temperature.The supernatant liquid that inclines, the centrifuge washing lower sediment is collected the supernatant liquid in the centrifuge washing process, obtains silver ions compound TiO 2 sol.
Get 92 parts of above-mentioned silver ions composite titanium dioxide Nano sols, under agitation after wherein adding 8 parts cetyl trimethylammonium bromide, be sprayed on the pottery of biscuiting, after the drying at room temperature, in the muffle furnace in 1050 ℃ of constant temperature after 3 hours, naturally cooling.Obtain having the silver ions dioxide composite titanium film of light purification function at ceramic surface.
Claims (10)
1. method that on ceramic surface, forms composite metal-TiO 2 film with light purification function, it is characterized in that: this method may further comprise the steps, and related amount is in parts by weight:
(1) under agitation, in 20～100 parts metal composite titanium dioxide nano particle colloidal sol, add 0～80 part deionized water and 0～10 part tensio-active agent, stir;
(2) colloidal sol with step (1) is sprayed at ceramic surface, and air drying is again in 50～300 ℃ of dryings 10 minutes～5 hours;
Or the colloidal sol of step (1) is sprayed at the ceramic surface of biscuiting, air drying;
(3), be 300～1300 ℃ of following constant temperature 10 minutes～10 hours in temperature with the above-mentioned ceramic that is covered with metal composite titanium dioxide nano particle film;
The composition of described metal composite titanium dioxide nano particle and content are:
Metal ion 0.005～5 weight part
Titanium dioxide 95～100 weight parts.
2. the method for claim 1, it is characterized in that: described step (2) is more than 1 time.
3. the method for claim 1, it is characterized in that: described tensio-active agent is polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, sodium laurylsulfonate or cetyl trimethylammonium bromide.
4. the method for claim 1, it is characterized in that: described metal composite titanium dioxide nano particle colloidal sol is obtained by following method, and this method may further comprise the steps, and related amount is in parts by weight:
(1) gets 15～65 parts of titanium tetrachlorides and be dissolved in 35～85 portions of frozen water, stir, obtain titanium tetrachloride aqueous solution;
(2) under stirring fast, the adding transition metal salt is dissolved in 0.1～30 part of the solution that generates in 90～100 parts the deionized water in the titanium tetrachloride aqueous solution of 10～50 parts of steps (1), and this transition metal salt is by the complexing agent complexing; Stir constant temperature under 50～400 ℃ of temperature;
(3) naturally cooling, the supernatant liquid that inclines, centrifuge washing lower sediment; Collect the supernatant liquid that obtains in the centrifuge washing process, obtain metal composite titanium dioxide nano particle colloidal sol.
5. method as claimed in claim 4 is characterized in that: described step (2) further added 30～85 parts of deionized waters before constant temperature.
6. method as claimed in claim 4 is characterized in that: described step (2) constant temperature 0.5～7 hour.
7. method as claimed in claim 4 is characterized in that: described complexing agent is ammoniacal liquor, oxalate, thiosulphate or thiocyanate-.
8. as claim 1 or 4 described methods, it is characterized in that: described metal is iron, nickel, platinum, iridium, palladium, silver, zinc or copper transition metal.
9. method as claimed in claim 4 is characterized in that: described salt is transition metal chloride or metal nitrate.
10. as claim 1 or 4 any described methods, it is characterized in that: the particle diameter of described titanium dioxide nano-particle is 3～50 nanometers.
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| CN 01131336 CN1197662C (en) | 2001-09-24 | 2001-09-24 | Method for forming metal composite titanium dioxide nano particle film on ceramic surface |
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| CN 01131336 CN1197662C (en) | 2001-09-24 | 2001-09-24 | Method for forming metal composite titanium dioxide nano particle film on ceramic surface |
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| CN100425573C (en) * | 2004-02-27 | 2008-10-15 | 申佑芝 | Mfg. method of nano ceramics |
| CN1312050C (en) * | 2004-10-28 | 2007-04-25 | 上海交通大学 | Method for light catalytic degrading carbamate pesticide in water |
| CN1305588C (en) * | 2005-03-21 | 2007-03-21 | 付飘敏 | Preparation method of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide |
| CN101070403B (en) * | 2007-06-07 | 2010-05-19 | 聊城华塑工业有限公司 | Blow-moulded film interface molecular film and production process |
| CN102784633B (en) * | 2011-05-17 | 2016-08-03 | 李文发 | Photocatalyst TiO2supported body manufacture method and the manufacture of photocatalyst air purifying machine |
| CN102784645A (en) * | 2011-05-17 | 2012-11-21 | 王东宁 | Metal particle combination TiO2 photocatalyst reinforcement anti-bacterial composition and preparation method thereof |
| CN102441376A (en) * | 2011-10-25 | 2012-05-09 | 通化师范学院 | Photoactivation preparation method for nano-AgCl/Ag visible-light catalyst |
| CN105478114B (en) * | 2015-12-01 | 2018-04-03 | 南京工业大学 | Preparation method of palladium catalyst loaded on ceramic membrane |
| CN109111243B (en) * | 2018-09-20 | 2020-12-11 | 界首永恩机电科技有限公司 | Method for spraying composite copper powder on surface of ceramic artwork |
| CN113475521A (en) * | 2021-07-08 | 2021-10-08 | 安徽江淮汽车集团股份有限公司 | Composite efficient antibacterial automobile disinfectant and preparation method thereof |
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