CN106311343A - Low-temperature preparation method of nonalcoholic visible light photocatalysis nano-dispersion - Google Patents
Low-temperature preparation method of nonalcoholic visible light photocatalysis nano-dispersion Download PDFInfo
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- CN106311343A CN106311343A CN201510339734.7A CN201510339734A CN106311343A CN 106311343 A CN106311343 A CN 106311343A CN 201510339734 A CN201510339734 A CN 201510339734A CN 106311343 A CN106311343 A CN 106311343A
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Abstract
The invention relates to a low-temperature preparation method of a nonalcoholic visible light photocatalysis nano-dispersion, and belongs to the field of production of visible light photocatalytic indoor air purification products. The nano-dispersion is suitable for being supported on a cloth substrate in vehicles in a spray mode. The method comprises the following steps: constructing an acidic aqueous solution with the pH value of 1, adding a soluble antibacterial component, directly adding an organic titanium precursor and a visible light photocatalysis component, cycling nano-colloid mill cooperated hydrolysis, adding initiation crystals, carrying out normal pressure heating in a rotary evaporator, carrying out reduced pressure rotary evaporation, diluting, adjusting the obtained diluted solution to be weakly acidic, and adding a surfactant. The dispersion prepared by using the rotary evaporator has no peculiar smell and is suitable for being used as a fragrant photocatalysis product base liquid, cooperation of the colloid mill with hydrolysis makes the method be suitable for industrialization, the low-temperature preparation mode reduces the cost, the dilution step improves the use safety, no white black spots are formed in the spraying process, and the added visible photocatalysis component makes the dispersion has visible light response.
Description
Technical field
The present invention relates to the low temperature preparation method of a kind of no-alcohol type visible light photocatalysis nano dispersion fluid, be suitable for visible light photocatalysis indoor air purification product preparation field, be particularly suited for being carried on spraying method the cloth base material of vehicle interior.
Background technology
Photocatalysis is a kind of green technology having important application prospect at environmental area, and it is that air cleaning, purification of water quality provide a kind of new resolving ideas.The most American-European, Japan develops multiple more ripe light catalytic purifying product, the Hydrotect series of products being suitable to air cleaning that such as pottery machine (strain) comprehensive study of Japan east is developed, and for example the LiquidLens UPW water purification system etc. of U.S. Entegris ultra-pure water company exploitation.
The preparation of photocatalyst is the basis of photocatalysis technology application, and its syntheti c route can be divided into Inorganic synthese and organic synthesis by the classification of titanium source.The pertitanic acid that Inorganic synthese obtains because having that colloid size is big, poor dispersion, just must can have the problems such as photocatalysis characteristic, so people's more employing organic synthesis mode prepares photocatalyst by high temperature sintering.
Organic synthesis often uses titanium tetrachloride, tetraethyl titanate, metatitanic acid four n-propyl, tetraisopropyl titanate or butyl titanate as organic titanium source.The titanium oxide dispersion usually taste of above-mentioned organic titanium source hydrolysis gained stimulates, this is because 1. may add certain alcohols solvent during synthesis；2. may add hydrolysis inhibitor acetylacetone,2,4-pentanedione etc.；3. organic titanium source hydrolyzate contains alcohols volatile products；4. add acid or alkali.So containing stimulating alcohol taste or the very difficult basic components liquid as photocatalysis daily purification product of the dispersion liquid containing other bad smell, it is not only due to when developing various odor types and purifying product to cover fragrance, it is often more important that consumer will not buy this type of purification product that the smell is awful.
Dropwise operation is usually used in the hydrolysis of organic titanium source, if rate of addition is the slowest, organic titanium source easily solidifies because meeting air and steam, then can form long solids at dropping tip；If rate of addition crosses block, form cake mass the most in aqueous, however it is necessary that and could eliminate through long agitation.Sometimes through addition alcohols by organic titanium source diluting, to reduce hydrolysis rate, but it is introduced into solvent odorous.Prepare across to an industrial bottleneck so the lifting of preparation speed is laboratory.
The colloid size of organic titanium source hydrolysis gained and selected catalyst performance qualitative correlation: if using acidic catalyst, organic titanium source hydrolyzes by H3O+Electrophilic mechanism cause, hydrolysis easily carry out, gained micelle is less, it is easy to dispersion；If use base catalyst, hydrolysis is by OH−Nucleophilic displacement of fluorine causes, and polycondensation speed is greatly improved, and gained micelle is bigger.Acidic catalyst method is all selected so being typically prepared, but the liquid obtained, and acid strong user health of also giving brings potential hazard.
Titaniferous amount is not The more the better.If the titaniferous amount comparison being applicable to the photocatalysis dispersion liquid of spraying is high, such as 1%, can form the spot of white at dark base material, this will affect the visual experience of base material.
It addition, prepare gained photocatalyst basal liquid by the hydrolysis of organic titanium source, it is only capable of producing strong response under ultraviolet light, produces hydroxyl radical free radical to remove depollution；And under visible light, be especially but difficult to work under faint visible ray, greatly limit the use of this type of photocatalyst.
Summary of the invention
The present invention provides the low temperature preparation method of a kind of no-alcohol type visible light photocatalysis nano dispersion fluid, can be obtained a kind of without alcohol, faintly acid visible light photocatalysis dispersion liquid by the method, it is sprayed on dark substrate surface in the way of spraying will not form substantially white spot.
The present invention uses following technical process:
(1) with distilled water as solvent, adding acidic catalyst, regulate pH=1, obtaining volume is V0Acid solution；
(2) in above-mentioned acid solution, add the antibacterial components of the amount 0.01 ~ 2% of relatively titania, strong stirring 1 ~ 5h；
(3) again oxytropism solution is directly added into relatively V01 ~ 10% organic titanium source and relatively titanium dioxide quality 0.05 ~ 1% visible light photocatalysis component, strong stirring 0.5h, coordinate processing with circular nanometer colloid mill, to hydrolysis completely；
(4) being added thereto to the P25 powder body of relatively titanium dioxide quality 0.01 ~ 0.1% again, in Rotary Evaporators, under the conditions of 55 ~ 80 ° of C, normal heating rotates 5 ~ 10h；
(5) by aforesaid liquid in 40 ~ 50 ° of C Rotary Evaporators negative pressure evaporation to V070 ~ 80%；
(6) add distilled water in above-mentioned concentrated solution to V07 ~ 12 times；
(7) pH to the 4-5 of aforesaid liquid is regulated.
(8) adding surfactant, its addition is the 0.1 ~ 1% of final mass.
Further, the acidic catalyst used in above-mentioned steps (1) can select a kind of in hydrochloric acid, nitric acid, phosphoric acid or any mixture between them.
Further, antibacterial components used in above-mentioned steps (2) can select a kind of in Zn class, Ag class, Cu compounds or any mixture between them, and the salt wherein chosen should not produce precipitation with the acidic catalyst used in above-mentioned steps (1).
Further, a kind of during tetraethyl titanate, metatitanic acid four n-propyl, tetraisopropyl titanate, butyl titanate can be selected in the organic titanium source used in above-mentioned steps (3) or any mixture between them.
Further, a kind of during the visible light catalytic component used in above-mentioned steps (3) can select Pt class, La class, Bi class, Co class, Ni compounds or any mixture between them.
Further, a kind of during the surfactant used in above-mentioned steps (8) can select Triton X-100, dodecylbenzene sodium sulfonate, dioctadecylamine hydrochlorate or any mixture between them.
The present invention starts to construct the environment of acidity, is hydrolyzed to little granule titanium for organic titanium source and prepares.Choose the salt of a kind of or the most several solubility in suitable Zn class, Ag class, Cu compounds, be sufficiently stirred for so that it is be full of sour environment, precipitation the most should not had to produce, construct the acid solution system of a metal ion.It is directly added into organic titanium source and visible light photocatalysis component again, under conditions of being sufficiently stirred for and shearing so that the salt apoplexy due to endogenous wind metal ion of the titanium elements in titanium source, the element in visible light photocatalysis component and above-mentioned solubility fully combines；In hydrolytic process, the unformed colloidal sol of visible ray titanium containing doped with metal elements can be formed.Adding a small amount of P25 powder brilliant as causing, unformed titanium colloidal sol converts to sharp titanium colloidal sol under suitably adding the gentle time.By-product alcohols in water and organic titanium source forms azeotropic mixture, and negative pressure heating rotation boils off suitable volume, removes alcohols to eliminate the special odor impact of solvent.Dilute and regulate colloidal sol pH, regulating wherein active constituent content and faintly acid so that spraying effect promotes and improves safety.Adding surfactant also makes spraying effect promote.
Present invention have the advantage that the visible light photocatalysis dispersion liquid utilizing Rotary Evaporators to process does not has abnormal flavour, be adapted as adding the basal liquid of the photocatalytic product of odor type；It is used in combination micelle mill by being directly added into titanate esters, it is adaptable to industrialization, production can be made to realize rapid；Low temperature preparation method makes production cost reduce；Solution is become faintly acid and reduces the concentration of titanium in dispersion liquid by last dilution step, improves the safety of use, will not form white spot during spraying；The visible light catalytic composition added makes the dispersion liquid of preparation have visible light photocatalysis effect.
Specific implementation method
In conjunction with specific embodiments, the present invention will be further described.
Embodiment 1
Appropriate 37% hydrochloric acid solution, the hydrochloric acid solution of configuration pH=1 is added in 100mL distilled water.It is subsequently adding the zinc chloride of 0.065g, strong stirring 2h.It is directly added into the tetraethyl titanate of 10mL and the tetraammineplatinum chloride of 0.002g, strong stirring 0.5h, coordinates processing with circular nanometer colloid mill.Add the P25 of 0.004g, under the conditions of 65 ° of C, process gained liquid 8h with Rotary Evaporators normal pressure.Aforementioned titaniferous liquid is evaporated to 70mL in Rotary Evaporators.Interpolation distilled water makes to mention and reaches 800mL, regulates pH to 4.Finally, the dodecylbenzene sodium sulfonate of 1mL is added.Obtain A liquid.
Embodiment 2
Appropriate 65% salpeter solution, the salpeter solution of configuration pH=1 is added in 250mL distilled water.It is subsequently adding the copper nitrate of 0.027g, strong stirring 1h.It is directly added into metatitanic acid four n-propyl and the cobalt acetate of 0.003g of 20mL, strong stirring 0.5h, coordinates processing with circular nanometer colloid mill.Add the P25 of 0.003g, under the conditions of 70 ° of C, process gained liquid 9h with Rotary Evaporators normal pressure.Aforementioned titaniferous liquid is evaporated to 200mL in Rotary Evaporators.Interpolation distilled water makes to mention and reaches 2000mL, regulates pH to 4.5.Finally, the Triton X-100 of 2mL is added.Obtain B liquid.
Embodiment 3
Appropriate 85% phosphoric acid solution, the phosphoric acid solution of configuration pH=1 is added in 500mL distilled water.It is subsequently adding the silver nitrate of 0.24g, strong stirring 1h.It is directly added into the butyl titanate of 25mL and the nickel nitrate of 0.003g, strong stirring 0.5h, coordinates processing with circular nanometer colloid mill.Add the P25 of 0.006g, under the conditions of 60 ° of C, process gained liquid 6h with Rotary Evaporators normal pressure.Aforementioned titaniferous liquid is evaporated to 400mL in Rotary Evaporators.Interpolation distilled water makes to mention and reaches 4000mL, regulates pH to 5.Finally, the dioctadecylamine hydrochlorate of 4mL is added.Obtain C liquid.
Embodiment 4
Taking A, B and C liquid of 100mL, in the bottle of fill forward (FWD) shower nozzle, shower nozzle specification is 24/410, and material is PP.20cm x 10cm non-woven fabrics selected by spray figure base material.At vertical dimension base material 20cm, carry out injection process, by every 100cm2Spray Fig. 3 time, each quantity for spray about 0.2mL.Using GB/T 23761-2009 standard detection aldehydes gas removal efficiency, employing wave-length coverage is 400-760nm, four tubular fluorescent lamps of power 8W, fid detector, and carrier gas is the high pure nitrogen of flow velocity 40mL/min, and acetaldehyde concentration is about 5.0mL/m3, flow is 50mL/min.A, B and C liquid acetaldehyde photocatalysis clearance is respectively 64.3%, and 72.4%, 67.8%.
Claims (6)
1. a low temperature preparation method for no-alcohol type visible light photocatalysis nano dispersion fluid, uses following technical process:
(1) with distilled water as solvent, adding acidic catalyst, regulate pH=1, obtaining volume is V0Acid solution；
(2) in above-mentioned acid solution, add the antibacterial components of the amount 0.01 ~ 2% of relatively titania, strong stirring 1 ~ 5h；
(3) again oxytropism solution is directly added into relatively V01 ~ 10% organic titanium source and relatively titanium dioxide quality 0.05 ~ 1% visible light photocatalysis component, strong stirring 0.5h, coordinate processing with circular nanometer colloid mill, to hydrolysis completely；
(4) being added thereto to the P25 powder body of relatively titanium dioxide quality 0.01 ~ 0.1% again, in Rotary Evaporators, under the conditions of 55 ~ 80 ° of C, normal heating rotates 5 ~ 10h；
(5) by aforesaid liquid in 40 ~ 50 ° of C Rotary Evaporators negative pressure evaporation to V070 ~ 80%；
(6) add distilled water in above-mentioned concentrated solution to V07 ~ 12 times；
(7) pH to the 4-5 of aforesaid liquid is regulated；
(8) adding surfactant, its addition is the 0.1 ~ 1% of final mass.
2. can select a kind of in hydrochloric acid, nitric acid, phosphoric acid or any mixture between them according to the acidic catalyst described in claim 1 step (1).
3. can select a kind of in Zn class, Ag class, Cu compounds or any mixture between them according to the antibacterial components described in claim 1 step (2), the salt wherein chosen should not produce precipitation with the acidic catalyst used in claim 2.
4. can select a kind of in tetraethyl titanate, metatitanic acid four n-propyl, tetraisopropyl titanate, butyl titanate or any mixture between them according to the organic titanium source described in claim 1 step (3).
5. can select a kind of in Pt class, La class, Bi class, Co class, Ni compounds or any mixture between them according to the visible light catalytic component described in claim 1 step (3).
6. can select a kind of in Triton X-100, dodecylbenzene sodium sulfonate, dioctadecylamine hydrochlorate or any mixture between them according to the surfactant described in claim 1 step (8).
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Citations (5)
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| CN1397377A (en) * | 2002-08-14 | 2003-02-19 | 清华大学 | Process for preparing photocatalytic TiO2 film used to clean water and air |
| CN1729145A (en) * | 2002-11-07 | 2006-02-01 | 萨斯提那普尔科技股份有限公司 | Titania-metal composite and method for preparation thereof, and film forming method using dispersion comprising the composite |
| CN1927949A (en) * | 2006-07-20 | 2007-03-14 | 厦门大学 | Method of preparing anatase type titanium dioxide dispersion at low temperature by hot-liquid method |
| JP2014084246A (en) * | 2012-10-23 | 2014-05-12 | Kri Inc | Production method of anatase type titanium oxide particle dispersion and anatase type titanium oxide thin film |
| CN104264450A (en) * | 2014-09-11 | 2015-01-07 | 苏州印丝特纺织数码科技有限公司 | Silk fabric anti-bacterial finishing agent and preparation method thereof |
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- 2015-06-18 CN CN201510339734.7A patent/CN106311343A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397377A (en) * | 2002-08-14 | 2003-02-19 | 清华大学 | Process for preparing photocatalytic TiO2 film used to clean water and air |
| CN1729145A (en) * | 2002-11-07 | 2006-02-01 | 萨斯提那普尔科技股份有限公司 | Titania-metal composite and method for preparation thereof, and film forming method using dispersion comprising the composite |
| CN1927949A (en) * | 2006-07-20 | 2007-03-14 | 厦门大学 | Method of preparing anatase type titanium dioxide dispersion at low temperature by hot-liquid method |
| JP2014084246A (en) * | 2012-10-23 | 2014-05-12 | Kri Inc | Production method of anatase type titanium oxide particle dispersion and anatase type titanium oxide thin film |
| CN104264450A (en) * | 2014-09-11 | 2015-01-07 | 苏州印丝特纺织数码科技有限公司 | Silk fabric anti-bacterial finishing agent and preparation method thereof |
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