CN1583249A - Preparing method of nanometer titania composite membrane for photocatalysis - Google Patents
Preparing method of nanometer titania composite membrane for photocatalysis Download PDFInfo
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- CN1583249A CN1583249A CN 200410022758 CN200410022758A CN1583249A CN 1583249 A CN1583249 A CN 1583249A CN 200410022758 CN200410022758 CN 200410022758 CN 200410022758 A CN200410022758 A CN 200410022758A CN 1583249 A CN1583249 A CN 1583249A
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Abstract
A composite nano-TiO2 membrane for photocatalysis is prepared through proportionally ixing tetrbutyl titanate with isopropanol, polyethanediol, distilled water and the aqueous solution of nitric acid while stirring, stirring at 50-80 deg.c, hydrolyzing to obtain TiO2 sol, adding nano-TiO2, grinding, coating the slurry on glass or glass fibres, drying and calcining.
Description
One, technical field
The present invention relates to a kind of preparation method who is used for light-catalysed nanometer titanium dioxide composite membrane, belong to the preparation field of light-catalysed nanometer titanium dioxide composite membrane.
Two, background technology
TiO
2Be the n type semiconductor of broad stopband, absorb the light time of energy greater than 400nm, electronics transits to conduction band from valence band, thereby produces electron hole pair effectively.TiO
2After being made into nano particle, because particle diameter reduces to produce quantum size effect and because the nanometer that particle diameter reduces makes surface area increase several magnitude, make nano titanium oxide demonstrate optics special, that be different from body and electrical properties.But TiO
2Its application in photocatalysis field has been limited in the ultra-violet (UV) band that only can absorb sunshine.
Gratzel was published in " NATURE " in 1991 paper has proposed sensitization nanometer titanium dioxide titanium solar battery first, and it is a kind of novel inexpensive and high performance solar batteries, and its light anode is with TiO
2The nano particle sintering forms nano-porous films in the electro-conductive glass substrate, absorption one deck sensitizing dyestuff on perforated membrane then is the electro-conductive glass that is coated with Pt to electrode then, is I between two electrodes
2/ I
-Redox electrolytes matter.
Be used for light-catalysed TiO
2Require nanometer, porous, filming, make TiO
2Have high-specific surface area and adsorb more individual layer dye molecule, have only adsorbed close could produce effective sensitizing effect at the individual layer dye molecule of semiconductor surface.In addition, the surface roughness of nano-electrode is big, and sunshine is repeatedly reflection in rough surface, can be absorbed repeatedly by dye molecule, thereby improve the utilization rate of sunshine greatly.
Therefore, the specific area of titanium dioxide film has very big influence to the performance of battery, and the porous nano film of preparation bigger serface is the precondition that obtains efficient sensitization solar battery.The method for preparing at present the porous nano titanium deoxid film mainly contains two kinds:
Sol-gel process prepares film: the presoma hydrolysis with titanium dioxide earlier makes TiO
2Ultra-fine colloidal solution is then with brushing method or czochralski method, with TiO
2Ultra micron colloidal sol is transferred on the electro-conductive glass, prepares nano titanium dioxide film through super-dry and sintering.The adhesion that this method obtains titanium deoxid film and matrix is strong, but technology is loaded down with trivial details, reaches thickness (the about 10 μ m) TiO that photoelectricity transforms to be needed
2Film need repeatedly lift transfer and just can make, and the contraction that produces when dissolved glue film is dry usually causes film imperfect and inhomogeneous.In addition, be difficult to control the particle diameter of nano material, the porous of the film of preparation is relatively poor, and the reunion of powder is also relatively more serious; Simultaneously, because preparation process heating and cooling repeatedly, softening and cracking takes place in the glass basis of solar cell easily.The sol-gel method craft higher cost of nano titanium dioxide film that also causes of price complicated and TiO 2 precursor is higher.
Titanic oxide nano prepares film: at TiO
2Add suitable quantity of water and additive in the nano powder, through vibration, grinding, the titanium dioxide powder of agglomerated is dispersed into uniform slurry, and this slurry is coated on the electro-conductive glass, dry back high-temperature heat treatment.Prepare nano titanium oxide though directly use the price of titanium dioxide nano-particle to be lower than sol-gel process, it is relatively poor that this method prepares the adhesion of film, and thickness is also inhomogeneous.In order to improve adhesion, the repeatedly a spot of method system film of the employing that has has increased workload.
Chinese patent 01140225 discloses a kind of preparation method of nanometer crystal film, and employing coating-sintering-coating-method of sintering is repeatedly carried out again again.
The special Open 2002-222618 of Chinese patent 99806409 and Japan Patent discloses the preparation method of photocell with titanium deoxid film, mixes with titanium dioxide with binding agent and carries out serigraphy system film; Dry back high temperature sintering has overcome the problem that repeatedly is coated with sintering.But the residue of high polymer binder behind sintering that this technology is introduced can influence the photocatalysis effect.
Japan Patent Te Open 2002-145615 discloses a kind of TiO
2Method for manufacturing thin film without the nanometer titanium dioxide titanium valve, but is directly sprayed 70 times on high temperature heated glass substrate with TiO 2 precursor solution, and TiO 2 precursor forms titanium dioxide film in thermal decomposition.But this method needs a specially-made heating, cooling, spraying, sintering equipment, and owing to need continuous heating and cooling, causes being difficult to preparing continuously solar cel electrode.
Also have metal-organic chemical vapor deposition equipment method, magnetron sputtering method, anodic oxidation Hydrolyze method and hydro-thermal method etc. in addition.
But said method does not all relate to the influence problem of the technology of preparing of titanium deoxid film to adhesion, thickness evenness.
Three, summary of the invention
The objective of the invention is at the deficiencies in the prior art, and provide a kind of preparation method who can be used for light-catalysed nanometer titanium dioxide composite membrane, can make to combine between titanium dioxide and the matrix firmly and do not increase harmful substance in the titanium dioxide film, effectively improve the uniformity and the controllable thickness of nano titanium dioxide film simultaneously.
Purpose of the present invention is realized that by following technical measures wherein raw materials used umber is parts by weight except that specified otherwise.
1,100～150 parts of butyl titanates is added in 40～60 parts of the intensively stirred isopropyl alcohols, what add molecular weight 1500～20000 then contains 2.5～4 parts of 2wt% cetomacrogol 1000 part, 500～1000 parts of distilled water and 67wt% aqueous solution of nitric acid, continue for 50～80 ℃ to stir in temperature, hydrolysis made colloidal tio 2 solution in 120～240 minutes.
2, in 100～150 parts of the titanium dioxide powders of granularity 10～60nm add 1000 parts of above-mentioned colloidal tio 2 solution, ground 0.2～2 hour, make the composite mortar of nano-titanium dioxide powder and colloid.
3, the composite mortar with above-mentioned nano-titanium dioxide powder and colloid evenly is coated on the glass or glass fabric of cleaning, in 40 ℃～85 ℃ dryings of temperature, 500～550 ℃ of sintering of temperature 30～120 minutes, obtains to be used for light-catalysed nano titanium dioxide film.
The present invention has the following advantages:
1, the present invention has significantly improved the adhesion of titanium dioxide film and glass or glass fabric, has simplified the preparation technology of nano titanium dioxide film; Simultaneously can directly utilize the clear and definite titanic oxide nano of granularity, better controlled the particle diameter of nano titanium dioxide film; And shortcomings such as expensive TiO 2 precursor such as tetrabutyl titanate hydrolysis system film have been avoided using.
2, residuals did not influence light-catalysed effect after the present invention introduced additive and avoided sintering.
Four, the specific embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1: butyl titanate 100g+ isopropyl alcohol 40g+ molecular weight is the aqueous solution 2.8g that 1500 the aqueous solution 1000g+ distilled water 1000g+ that contains the 2wt% polyethylene glycol contains 67wt% nitric acid, add in the container mix, stirring and hydrolysis make colloidal tio 2 solution.In the titanium dioxide powder 130g of granularity 40nm, add the above-mentioned colloidal tio 2 solution of 1000g, ground 30 minutes, be prepared into the composite mortar of nano-titanium dioxide powder and colloid.This composite mortar is uniformly coated on glass, through 40 ℃ of dryings, 510 ℃ of high temperature sinterings 30 minutes acquire nano titanium dioxide film.The bond strength of test membrane and glass sees table 1 for details.
Embodiment 2: with butyl titanate 120g+ isopropyl alcohol 50g+ molecular weight is the aqueous solution 3g that 5000 the aqueous solution 1000g+ distilled water 800g+ that contains the 2wt% polyethylene glycol contains 67wt% nitric acid, adds that container mixes, stirring and hydrolysis make colloidal tio 2 solution.In the titanium dioxide powder 120g of granularity 30nm, add the above-mentioned colloidal tio 2 solution of 1000g, ground 30 minutes, be prepared into the composite mortar of nano-titanium dioxide powder and colloid.This composite mortar is uniformly coated on glass, through 50 ℃ of dryings, 550 ℃ of high temperature sinterings 30 minutes acquire nano titanium dioxide film.The bond strength of test membrane and glass sees table 1 for details.
Embodiment 3: with butyl titanate 150g+ isopropyl alcohol 60g+ molecular weight is the aqueous solution 4g that 10000 the aqueous solution 1000g+ distilled water 500g+ that contains the 2wt% polyethylene glycol contains 67wt% nitric acid, adds that container mixes, stirring and hydrolysis make colloidal tio 2 solution.In the titanium dioxide powder 110g of granularity 20nm, add the above-mentioned colloidal tio 2 solution of 1000g, ground 45 minutes, be prepared into the composite mortar of nano-titanium dioxide powder and colloid.This composite mortar is uniformly coated on glass, through 85 ℃ of dryings, 500 ℃ of high temperature sinterings 120 minutes acquire nano titanium dioxide film.The bond strength of test membrane and glass sees table 1 for details.
Embodiment 4: with butyl titanate 150g+ isopropyl alcohol 60g+ molecular weight is the aqueous solution 4g that 20000 the aqueous solution 1000g+ distilled water 600g+ that contains the 2wt% polyethylene glycol contains 67wt% nitric acid, adds that container mixes, stirring and hydrolysis make colloidal tio 2 solution.In the titanium dioxide powder 150g of granularity 60nm, add the above-mentioned colloidal tio 2 solution of 1000g, ground 60 minutes, be prepared into the composite mortar of nano-titanium dioxide powder and colloid.This composite mortar is uniformly coated on the glass fabric, and through 80 ℃ of dryings, 550 ℃ of high temperature sinterings 40 minutes acquire nano titanium dioxide film.The bond strength of test membrane and glass fabric sees table 1 for details.
Embodiment 5: with butyl titanate 130g+ isopropyl alcohol 53g+ molecular weight is the aqueous solution 3.5g that 20000 the aqueous solution 1000g+ distilled water 500g+ that contains the 2wt% polyethylene glycol contains 67wt% nitric acid, adds that container mixes, stirring and hydrolysis make colloidal tio 2 solution.In the titanium dioxide powder 100g of granularity 10nm, add the above-mentioned colloidal tio 2 solution of 1000g, ground 30 minutes, be prepared into the composite mortar of nano-titanium dioxide powder and colloid.This composite mortar is uniformly coated on the glass fabric, and through 60 ℃ of dryings, 520 ℃ of high temperature sinterings 50 minutes acquire nano titanium dioxide film.The bond strength of test membrane and glass sees table 1 for details.
Comparative example 1: by butyl titanate 100g+ isopropyl alcohol 60g+ molecular weight is the aqueous solution 3g that the aqueous solution 1000g+ distilled water 1000g+ that contains the 2wt% polyethylene glycol of 1300-1500 contains 67wt% nitric acid, be hydrolyzed and make colloidal tio 2 solution, film on glass, 60 ℃ lift once in colloidal tio 2 solution after the oven dry down again, dry so repeatedly-lift 10 times, then 500 ℃ of high temperature sinterings 1 hour.The bond strength of test membrane and glass the results are shown in Table 1.The film bond strength that obtains with the method gets relatively good, but extremely inhomogeneous, and reason is attached to the colloidal solution of glass surface because capillary effect, and the phenomenon of automatic contraction is arranged, and the local rete that brings thus is too thick and cause being easy to split.The results are shown in Table 1.
Comparative example 2: granularity is that the titanium dioxide 120g+ molecular weight of 40nm is the aqueous solution 180g of 20000 2wt% polyethylene glycol, grinds 90min; Film on glass 60 ℃ of oven dry, 500 ℃ of following sintering 1h.The bond strength of test membrane and glass the results are shown in Table 1.
Comparative example 3: granularity is that the titanium dioxide 120g+ molecular weight of 30nm is 5000 the aqueous solution 160g that contains the 2wt% polyethylene glycol, grinds 70min; Film on glass fabric 60 ℃ of oven dry, 500 ℃ of following sintering 1 hour.The bond strength of test membrane and glass the results are shown in Table 1.
As seen from Table 1, the titanic oxide nano-membrane of technology preparation of the present invention, the adhesion of nanometer film/glass or glass fabric obviously increases; In addition, outward appearance is more level and smooth, do not have defectives such as local contraction, shows that adhesion between the nano particle is also strengthened and strengthens; Simultaneously, preparation technology is easier.
Table 1
Claims (1)
1, a kind of preparation method who is used for light-catalysed nanometer titanium dioxide composite membrane, its spy is:
(1) with butyl titanate 100～150 weight portion, under strong agitation, add isopropyl alcohol 40～60 weight portions, molecular weight is 1500～20000 contains 2wt% cetomacrogol 1000 weight portion, distilled water 500～1000 weight portions and contain 67wt% aqueous solution of nitric acid 2.5～4 weight portions, continue for 50～80 ℃ to stir in temperature, hydrolysis made colloidal tio 2 solution in 120～240 minutes
(2) with titanium dioxide powder 100～150 weight portions of granularity 10～60nm, add in above-mentioned colloidal tio 2 solution 1000 weight portions, ground 0.2～2 hour, make the composite mortar of nanometer titanium dioxide titanium valve and colloid,
(3) composite mortar with above-mentioned nanometer titanium dioxide titanium valve and colloid evenly is coated on the glass or glass fabric of cleaning, in 40 ℃～85 ℃ dryings of temperature, 500～550 ℃ of sintering of temperature 30～120 minutes, obtain to be used for light-catalysed nanometer titanium dioxide composite membrane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415660C (en) * | 2005-10-27 | 2008-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Process for mfg. equipment for treating pollution water body |
| CN101250273B (en) * | 2008-03-26 | 2011-01-12 | 华东师范大学 | Method for preparing nano ZnO/polyvinyl acetate composite film |
| CN102231304A (en) * | 2011-03-28 | 2011-11-02 | 彩虹集团公司 | Method for preparing nano TiO2 (titanium dioxide) pastes |
| CN108636391A (en) * | 2018-04-29 | 2018-10-12 | 华中科技大学 | A kind of load type titanium dioxide photocatalytic material and preparation method thereof |
| CN113842707A (en) * | 2021-09-17 | 2021-12-28 | 兴源环境科技股份有限公司 | High-flux anti-sticking filter cloth for blue algae mud dehydration and preparation method thereof |
-
2004
- 2004-06-10 CN CN 200410022758 patent/CN1583249A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415660C (en) * | 2005-10-27 | 2008-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Process for mfg. equipment for treating pollution water body |
| CN101250273B (en) * | 2008-03-26 | 2011-01-12 | 华东师范大学 | Method for preparing nano ZnO/polyvinyl acetate composite film |
| CN102231304A (en) * | 2011-03-28 | 2011-11-02 | 彩虹集团公司 | Method for preparing nano TiO2 (titanium dioxide) pastes |
| CN108636391A (en) * | 2018-04-29 | 2018-10-12 | 华中科技大学 | A kind of load type titanium dioxide photocatalytic material and preparation method thereof |
| CN113842707A (en) * | 2021-09-17 | 2021-12-28 | 兴源环境科技股份有限公司 | High-flux anti-sticking filter cloth for blue algae mud dehydration and preparation method thereof |
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