CN101654863A - Method for preparing fiber fabrics with self-cleaning property - Google Patents
Method for preparing fiber fabrics with self-cleaning property Download PDFInfo
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- CN101654863A CN101654863A CN200910195787A CN200910195787A CN101654863A CN 101654863 A CN101654863 A CN 101654863A CN 200910195787 A CN200910195787 A CN 200910195787A CN 200910195787 A CN200910195787 A CN 200910195787A CN 101654863 A CN101654863 A CN 101654863A
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Abstract
The invention relates to a method for preparing fiber fabrics with self-cleaning property in the field of nano photocatalysis, which comprises the following steps: firstly, dissolving a titanium precursor in alcohol to form a solution A, dipping the solution A in diluted hydrogen nitrate during severe stirring, continuously stirring, standing to obtain a solution B, wherein the volume ratio of thetitanium precursor to the alcohol to the diluted hydrogen nitrate is 1:(2-10):(20-80); and secondly, immersing the fiber fabrics into the solution B, and thermally treating to obtain the fiber fabrics with self-cleaning property. In the method, high-activity anatase hydrosol is obtained through longer-time stirring and standing for gelatification in low-temperature and acid condition, the fiber fabrics with self-cleaning property is obtained by the immersion of the fiber fabrics, and the fiber fabrics can be applied to the environment field and the medical field.
Description
Technical field
That the present invention relates to is a kind of preparation method of conductor photocatalysis technical field, and particularly a kind of preparation has the method for the fabric of self-cleaning performance.
Background technology
Raw material-titanium dioxide that the titanium dioxide semiconductor photocatalysis oxidation technique uses: cheap, stable performance, nontoxic non-corrosiveness; This technology can utilize solar energy to be the energy, and reaction condition gentleness, easy and simple to handle, non-secondary pollution.Dyestuff wherein, surfactant, organohalogen compounds, agricultural chemicals, cyanide, phenols, Polychlorinated biphenyls and polycyclic aromatic hydrocarbon etc. can both be by catalytic degradation, decolouring, detoxification, mineralising are the inorganic molecules material effectively.Titania powder is difficult to reclaim makes this technology be difficult to large-scale application.
In the present stage practical application, TiO
2Catalysis material has been used for fields such as the purifier, self-cleaning glass surface, antibiotic photocatalysis ceramics face brick of water and air, has produced huge economy, environment and social benefit.But titanium dioxide mainly is fixed on the resistant to elevated temperatures matrix such as glass, silica, stainless steel, alundum (Al, in immobilization process, need high temperature, need a large amount of energy consumptions on the one hand, increase cost, on the other hand, high-temperature process makes titanium dioxide be difficult to the fixing of matrix a little less than temperature resistant capability such as rubber, fiber etc.Load TiO on glass fibre or the carbon fiber
2The existing a large amount of report of functional material, but relate to the follow-up high-temperature heat treatment of the conventional amorphous predecessor of collosol and gel.The research of the photo-catalysis functionization of fabric is less, but has significant realistic price.And the photo-catalysis functionization of fabric relates to low temperature preparation height crystallization TiO
2There is certain difficulty in hydrosol technology.
Find through literature search prior art, Daoud, W.A. wait to have delivered to be entitled as " Nucleationand Growth of Anatase Crystallites on Cotton Fabrics at Low Temperatures " (nucleation of anatase crystal grain and growth under the cotton fiber surface low-temperature) literary composition, relate in the literary composition and adopt unbodied TiO 953～955 pages of " Journal of CeramicSociety " (ceramic association journal) 2004 the 5th phases
2After the colloidal sol load, obtain anatase crystal grains 180 ℃ of hydrothermal treatment consists, but subsequent heat treatment has not only increased loaded down with trivial details operation, and may since bubble produce and the TiO of perturbation load
2Nano particle makes it desorption.Therefore studying the anatase crystal grain that simple low temperature prepares crystallization is the prerequisite of fabric photo-catalysis functionization.Wang, J.Y. wait to have delivered and be entitled as " A simple new way to prepare anatase TiO2hydrosol with high photocatalytic activity " (a kind of straightforward procedure for preparing the high activity anatase tio2 hydrosol) literary composition at " Semiconductor Science and Technology " (semiconductor science and technology) the 8th phase L36～L39 page or leaf in 2005, the method of amorphous sediment 80 ℃ of gels under acid condition has been proposed, however the TiO of this method preparation
2Concentration is lower, is not suitable for the load in fabric surface, and follow-up acid and heat treatment are all with damaged fiber.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of preparation to have the method for the fabric of self-cleaning performance.Method of the present invention is under low temperature and acid condition, stirring by the long period and leave standstill and carry out gel and handle, obtain the high activity anatase hydrosol, impregnation process by fabric obtains fabric with automatically cleaning ability subsequently, and this fabric both can be applicable to environmental area and at medical domain.
The present invention realizes that by following technical scheme method of the present invention comprises the steps:
Step 1 is dissolved in the titanium precursor thing in the alcohol, forms solution A, under vigorous stirring solution A is added drop-wise in rare nitric acid, continues to stir, and leaves standstill, and gets solution B; Wherein, titanium precursor thing: alcohol: the volume ratio of rare nitric acid is: 1: (2～10): (20～80);
Step 2 is immersed in fabric in the solution B, and heat treatment must have the fabric of self-cleaning performance.
In the step 1, described titanium precursor thing is the mixing of a kind of in the following material or two kinds: butyl titanate, tetraisopropyl titanate and tetraethyl titanate.
In the step 1, described alcohol is ethanol, isopropyl alcohol or ethylene glycol.
In the step 1, the concentration of described rare nitric acid is 0.01～0.1M.
In the step 1, described lasting stirring is for stirring 24～72h.
In the step 1, described leaving standstill to lucifuge left standstill for 1～10 week.
In the step 2, described fabric will carry out pre-treatment, is specially: earlier fabric was washed with washing agent, second alcohol and water successively before submergence, afterwards oven dry.
In the step 2, described fabric will carry out pre-treatment, be specially: fabric is immersed in 10～30min in the aqueous solution of washing agent, the temperature of the aqueous solution is 50～80 ℃, spend the deionised water fabric afterwards to remove washing agent, with fiber sonicated 5～15min in ethanol, spend the deionised water fabric afterwards to remove ethanol, 50～70 ℃ of oven dry down.
In the step 2, described submergence is specially: submergence 1～10min.
In the step 2, described heat treatment is: fabric is placed 60 ℃ of oven dry down, dry by the fire 5～10min down at 100 ℃ afterwards, heat 3h at last in 70～90 ℃ deionized water, middle displacement deionized water 4～6 times.
Compared with prior art, the present invention has following beneficial effect: preparation method's production cost of the present invention is low, and preparation flow is simple, has the prospect of large-scale industrial production; And the fiber with automatically cleaning ability can reuse, as being covered when influencing the photocatalysis effect by solid matters such as mud when fiber surface in the water treatment procedure, only need wash the fiber water, just can utilize once more, can solve the problem that titanium dioxide optical catalyst is difficult to recycle easily like this.
Description of drawings
Fig. 1 is the untreated cotton and the uv-visible absorption spectra comparison diagram of embodiment 1 preparation cotton;
Fig. 2 is the degradation effect figure of the cotton of embodiment 1 preparation to methyl orange dye;
Fig. 3 is the influence figure of the cotton of embodiment 4 preparations to bacterial growth.
The specific embodiment
Following example will the invention will be further described in conjunction with the accompanying drawings.Present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
Step 1, the 5ml butyl titanate is blended in the 10ml ethanol, form solution, under intense agitation, in the 400ml 0.01M salpeter solution that solution dropwise is added drop-wise to, add water, be prepared into the TiO 2 sol that final volume is 450ml, continue to stir 24h, lucifuge left standstill for 1 week, obtained transparent TiO 2 sol;
Step 2 with 50 ℃ of aqueous solution soaking 30min of washing agent, is removed washing agent with deionized water with cotton (natural fabric) afterwards, uses ethanol supersound washing 5min again, and water is rinsed well, 50 ℃ of dryings.The cotton of handling is immersed in 1min in the TiO 2 sol, place 60 ℃ of baking ovens to remove solvent then, at 100 ℃ of following 5min, fiber after the coating is 3h in 70 ℃ of hot water, middle displacement deionized water 4 times, get rid of the not TiO 2 particles of secure bond of fiber surface, must have the cotton of self-cleaning performance.
The self-cleaning performance test that fiber had characterizes its photocatalysis to degrade organic matter performance by the organic dyestuff in the decomposition water under the illumination, by in liquid and solid medium the growth effect of bacterium being measured its antibiotic and sterilizing performance.
The photocatalysis to degrade organic matter experiment utilizes the photo catalysis reactor of 100ml to carry out at normal temperatures and pressures, reactor lower part has the netted interlayer of porous, the magnetic force rotor can rotate freely below the interlayer, its detailed process is: the fiber of 4cm * 4cm carried titanium dioxide entirely is placed on the interlayer of reactor, the methyl orange solution 50ml of measuring the 10mg/L for preparing then joins in the photo catalysis reactor, powerful magnetic agitation.Allow the interior titanium dioxide of phenol and reactor reach adsorption equilibrium before the photocatalysis experiment.Opening 1000W xenon lamp (optical filter that has 420nm) before, this concentration keeps constant always.Initial temperature in the reactor is 1 ℃ in 25 soil.For making reactor temperature constant, reactor is equipped with circulating water cooling device outward.Adopt powerful magnetic agitation in the course of reaction in the reactor always.Methyl orange concentration adopts spectrophotometry, and reaction is carried out the every 30min sampling in back once, measures the methyl orange change in concentration.Along with the carrying out of light-catalyzed reaction, methyl orange concentration descends gradually, and this degradation reaction is first order reaction, meets first-order kinetics equation ln (C
0/ C
t)=kt, C
0Be initial methyl orange concentration, C
tMethyl orange concentration when proceeding to t for reaction, k is a first-order kinetics apparent speed constant.
The implementation result of present embodiment: Fig. 1 is the comparison diagram of uv-visible absorption spectra of the cotton of the cotton do not handled and present embodiment preparation.As can be seen from the figure, the cotton of not handling does not absorb sunshine, and the cotton of carried titanium dioxide partly has strong assimilation effect to ultraviolet light.Fig. 2 is the TiO of 4cm * 4cm present embodiment preparation
2Load from the degradation effect figure of clean cotton to methyl orange dye, as can be seen from the figure, directly compare with methyl orange at the blank sample of UV-irradiation, the cotton of not handling does not have facilitation to the degraded of methyl orange, and the cotton of present embodiment preparation has the performance of tangible catalytic degradation methyl orange, and illumination 3h methyl orange clearance reaches 60%.
Embodiment 2
Step 1, the 5ml tetraisopropyl titanate is blended in the 50ml isopropyl alcohol, form solution, under intense agitation, in the salpeter solution of the 100ml 0.1M that solution dropwise is added drop-wise to, be prepared into the TiO 2 sol that final volume is 150ml, continue to stir 48h, lucifuge left standstill for 5 weeks, obtained transparent TiO 2 sol;
Step 2 with 80 ℃ of aqueous solution soaking 10min of washing agent, is removed washing agent with deionized water with cotton (natural fabric) afterwards, uses alcohol supersound washing 15min again, and water is rinsed well, 70 ℃ of dryings.The cotton of handling is immersed in 5min in the TiO 2 sol, place 60 ℃ of baking ovens to remove solvent then, at 100 ℃ of following 5min, fiber after the coating is 3h in 70 ℃ of hot water, middle displacement deionized water 6 times, get rid of the not TiO 2 particles of secure bond of fiber surface, must have the cotton of self-cleaning performance.
The fiber of the implementation result of present embodiment: 4cm * 4cm carried titanium dioxide is in photocatalytic degradation 10mg/L methyl orange dye process, can degrade 63% methyl orange of illumination 3h, perhaps fiber submergence 1min in colloidal sol, coating 5 times repeatedly after the washing drying, the fiber of 4cm * 4cm carried titanium dioxide in photocatalytic degradation 10mg/L methyl orange dye process, can degrade 66% methyl orange of illumination 3h.
Embodiment 3
Step 1, in 5ml tetraethyl titanate 20ml ethylene glycol, form solution, under intense agitation, in the 200ml 0.02M salpeter solution that solution dropwise is added drop-wise to, add water, be prepared into the TiO 2 sol that final volume is 250ml, continue to stir 72h, lucifuge left standstill for 10 weeks, obtained transparent TiO 2 sol;
Step 2 with 50 ℃ of aqueous solution soaking 10min of washing agent, is removed washing agent with deionized water with terylene cloth (synthetic fiber) afterwards, uses ethanol supersound washing 5min again, and water is rinsed well, 50 ℃ of dryings.The cloth of handling is immersed in 10min in the TiO 2 sol, place 60 ℃ of baking ovens to remove solvent then, at 100 ℃ of following 10min, fiber after the coating is 3h in 90 ℃ of hot water, middle displacement deionized water 6 times, get rid of the not TiO 2 particles of secure bond of fiber surface, must have the cotton of self-cleaning performance.
The implementation result of present embodiment: with the fiber of the carried titanium dioxide of 4cm * 4cm present embodiment preparation in photocatalytic degradation 10mg/L methyl orange dye process, can degrade 70% methyl orange of illumination 3h.
Embodiment 4
Step 1 in 10ml ethanol, forms solution with the mixed liquor of 2ml butyl titanate and 3ml tetraisopropyl titanate, under intense agitation, in the 200ml 0.04M salpeter solution that solution dropwise is added drop-wise to, add water, be prepared into the TiO 2 sol that final volume is 250ml; Continue to stir 48h, lucifuge left standstill for 4 weeks, obtained transparent TiO 2 sol;
Step 2 with 60 ℃ of aqueous solution soaking 20min of washing agent, is removed washing agent with deionized water with cotton afterwards, uses alcohol supersound washing 5min again, and water is rinsed well, 70 ℃ of dryings.The cotton of handling is immersed in 1min in the TiO 2 sol, place 60 ℃ of baking ovens to remove solvent then, at 100 ℃ of following 5min, fiber after the coating is 3h in 80 ℃ of hot water, middle displacement deionized water 5 times, get rid of the not TiO 2 particles of secure bond of fiber surface, obtain having the cotton of self-cleaning performance.
The detailed process of antibiotic and sterilizing performance test is as follows: the fiber of coating of titanium dioxide is lain in the culture dish, pour the 30ml nutrient solution then into, sterilize in the high steam reactor, the cooling back is inoculated on solid-state culture medium, the growing state of observation bacterium after cultivating 30h under the clean hatch fluorescent lamp.
The implementation result of present embodiment: the culture dish of the fiber of present embodiment preparation being put into 30ml LB solid medium.Behind the inoculation Escherichia coli, normal temperature is cultivated under the super-clean bench fluorescent lamp, compares with the blank sample, and the Escherichia coli growth seriously is suppressed.Fig. 3 is the influence figures of embodiment 4 carried titanium dioxide cottons to the Escherichia coli growth, as can be seen from the figure, the Escherichia coli that are seeded in culture medium have upgrowth situation good, and have the Escherichia coli growth on the culture medium of carried titanium dioxide cotton to be suppressed below being seeded in.
Claims (10)
1, a kind of preparation has the method for the fabric of self-cleaning performance, it is characterized in that, comprises the steps:
Step 1 is dissolved in the titanium precursor thing in the alcohol, forms solution A, under vigorous stirring solution A is added drop-wise in rare nitric acid, continues to stir, and leaves standstill, and gets solution B; Wherein, titanium precursor thing: alcohol: the volume ratio of rare nitric acid is: 1: (2～10): (20～80);
Step 2 is immersed in fabric in the solution B, and heat treatment must have the fabric of self-cleaning performance.
2, preparation according to claim 1 has the method for the fabric of self-cleaning performance, it is characterized in that, in the step 1, described titanium precursor thing is the mixing of a kind of in the following material or two kinds: butyl titanate, tetraisopropyl titanate and tetraethyl titanate.
3, preparation according to claim 1 has the method for the fabric of self-cleaning performance, it is characterized in that, in the step 1, described alcohol is ethanol, isopropyl alcohol or ethylene glycol.
4, preparation according to claim 1 has the method for the fabric of self-cleaning performance, it is characterized in that, in the step 1, the concentration of described rare nitric acid is 0.01～0.1M.
5, preparation according to claim 1 has the method for the fabric of self-cleaning performance, it is characterized in that, in the step 1, described lasting stirring is for stirring 24～72h.
6, preparation according to claim 1 has the method for the fabric of self-cleaning performance, it is characterized in that, in the step 1, described leaving standstill to lucifuge left standstill for 1～10 week.
7, preparation according to claim 1 has the method for the fabric of self-cleaning performance, it is characterized in that in the step 2, described fabric will carry out pre-treatment, be specially: before submergence, earlier fabric is washed with washing agent, second alcohol and water successively, afterwards oven dry.
8, preparation according to claim 7 has the method for the fabric of self-cleaning performance, it is characterized in that, in the step 2, described fabric will carry out pre-treatment, is specially: fabric is immersed in 10～30min in the aqueous solution of washing agent, the temperature of the aqueous solution is 50～80 ℃, spend the deionised water fabric afterwards to remove washing agent, with fiber sonicated 5～15min in ethanol, spend the deionised water fabric afterwards to remove ethanol, 50～70 ℃ of oven dry down.
9, preparation according to claim 1 has the method for the fabric of self-cleaning performance, it is characterized in that, in the step 2, described submergence is specially: submergence 1～10min.
10, preparation according to claim 1 has the method for the fabric of self-cleaning performance, it is characterized in that, in the step 2, described heat treatment is: fabric is placed 60 ℃ of oven dry down, dry by the fire 5～10min down at 100 ℃ afterwards, at last in 70～90 ℃ deionized water, heat 3h, middle displacement deionized water 4～6 times.
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| CN200910195787A CN101654863A (en) | 2009-09-17 | 2009-09-17 | Method for preparing fiber fabrics with self-cleaning property |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102587120A (en) * | 2012-01-06 | 2012-07-18 | 上海交通大学 | Self-cleaning cloth with decontamination and anti-bacteria functions in the sun and manufacturing method thereof |
| CN108138433A (en) * | 2015-09-30 | 2018-06-08 | 日本制纸株式会社 | The complex of cellulose fibre and inorganic particulate |
| CN108325511A (en) * | 2018-01-03 | 2018-07-27 | 湖北大学 | A kind of preparation method and application of nanometer of metastable state/anatase mixed crystal titanium oxide hydrosol |
| CN110183204A (en) * | 2019-06-10 | 2019-08-30 | 清华大学深圳研究生院 | A kind of water-permeable brick of load nano-titanium dioxide and preparation method thereof |
-
2009
- 2009-09-17 CN CN200910195787A patent/CN101654863A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102587120A (en) * | 2012-01-06 | 2012-07-18 | 上海交通大学 | Self-cleaning cloth with decontamination and anti-bacteria functions in the sun and manufacturing method thereof |
| CN102587120B (en) * | 2012-01-06 | 2013-09-11 | 上海交通大学 | Self-cleaning cloth with decontamination and anti-bacteria functions in the sun and manufacturing method thereof |
| CN108138433A (en) * | 2015-09-30 | 2018-06-08 | 日本制纸株式会社 | The complex of cellulose fibre and inorganic particulate |
| CN108325511A (en) * | 2018-01-03 | 2018-07-27 | 湖北大学 | A kind of preparation method and application of nanometer of metastable state/anatase mixed crystal titanium oxide hydrosol |
| CN108325511B (en) * | 2018-01-03 | 2021-06-08 | 湖北大学 | Preparation method and application of nano metastable state/anatase mixed crystal titanium oxide hydrosol |
| CN110183204A (en) * | 2019-06-10 | 2019-08-30 | 清华大学深圳研究生院 | A kind of water-permeable brick of load nano-titanium dioxide and preparation method thereof |
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Open date: 20100224 |