CN102198393B - Method for preparing mixed crystal nanometer titanium dioxide suspension from double precursors - Google Patents
Method for preparing mixed crystal nanometer titanium dioxide suspension from double precursors Download PDFInfo
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- CN102198393B CN102198393B CN201110083822A CN201110083822A CN102198393B CN 102198393 B CN102198393 B CN 102198393B CN 201110083822 A CN201110083822 A CN 201110083822A CN 201110083822 A CN201110083822 A CN 201110083822A CN 102198393 B CN102198393 B CN 102198393B
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- ticl
- titanium dioxide
- deionized water
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Abstract
The invention discloses a method for preparing mixed crystal nanometer titanium dioxide suspension from double precursors, which comprises the following steps of: (1) preparing TiCl4 solution and TiCl3 solution which have the titanium ion concentration of between 0.5 and 1.0 mol/L; (2) adding inorganic alkali solution into deionized water, adding mixed solution of the TiCl4 solution and the TiCl3solution until the pH value of the solution is between 1.0 and 2.5, crystallizing at the constant temperature of between 50 and 100 DEG C for 2 to 10 hours to obtain a white precipitate product, and filtering and washing to obtain a nanometer titanium dioxide wet sample; and (3) diluting the nanometer titanium dioxide wet sample by adding the deionized water, and performing ultrasonic dispersion to obtain the mixed crystal nanometer titanium dioxide suspension. The method is simple, the equipment requirement is low, the photocatalytic capacity of titanium dioxide generated by reaction is high, and the prepared suspension is stable. In addition, the suspension is prepared by using the wet sample directly, so that agglomeration can be reduced and prevented; and the suspension is diluted by adding the water and can be dispersed uniformly without ultrasonic.
Description
Technical field
The present invention relates to the inorganic material preparation method, refer to that specifically a kind of pair of presoma prepares the method for mixed crystal type nanometer titanium dioxide suspension, belongs to the material technology field.
Background technology
On n-type semiconductor monocrystal electrode, find the photoelectrocatalysis decomposing phenomenon of light decomposition water from A.Fjishima in 1972 and K.Hindan; 1976; Since Canada scientist Carey etc. carry out Research on degradation through nano titanium oxide to the extremely toxic substance Polychlorinated biphenyls; More scientific research person puts into the photocatalysis performance application study in environmental protection that utilizes nano titanium oxide, and the multiphase photocatalysis technology has caused research worker's concern.TiO
2Because of have photocatalytic activity height, good stability, to human non-toxic, advantage such as cheap; It is shown one's talent in many semiconductor light-catalysts, and application has spreaded all over the reduction, air cleaning, sterilization of degraded, the heavy metal ion of organic wastewater, numerous aspects such as antifog so far.The photocatalysis performance that nano titanium oxide the possessed organic matter that biology in water and air can't be degraded of not only can degrading is degraded to H with it
2O and CO
2, and can the inorganic metal ion that be present in the water deposited out, so nano titanium oxide is applied to organic dyestuff sewage, the control of environmental pollution such as pernicious gas, inorganic heavy metal ion in the air.In recent years, discover TiO with highlight catalytic active
2Majority is anatase and rutile duplex grain structure mutually, like the Degussa P of high catalytic activity
25TiO
2It is exactly the mixed crystal of " Anatase (80%)+Rutile (20%) ".It is because " mixed crystal effect " that the mixing crystal formation has high activity; Promptly in the superficial growth of anatase phase crystal very thin rutile phase crystallizing layer; Can promote the right separation of photoproduction in the Detitanium-ore-type crystal " electronics-hole " effectively; Reduce the interior mutually recombination probability of their bodies, and improve electron diffusion speed.More people is simple, with low cost and have a preparation method of the nano titanium oxide of the highlight catalytic active that commercial production is worth in a kind of technology of positive developmental research.
At present, to the more employing gas phase synthesis method of the preparation method of nano titanium oxide, water under high pressure thermal synthesis method sol-gel process etc.Though gas phase synthesis method can make the nano titanium dioxide powder with better quality, gas-phase reaction need make the material gasification, and energy consumption is higher.In addition, at high temperature moment the gas phase reaction process accomplished, the form of reactor, material, material import and export mode etc. are all had higher requirement, thereby bring a series of technical problems.The water under high pressure thermal synthesis method does not need high-temperature roasting just can directly obtain the good nano titanium oxide of crystal formation, though the formation of hard aggregation when having avoided high-temperature roasting.But this method complicated operation is high to equipment requirements.Other preparation method also exists the raw material majority that uses to be the higher titanium alkoxide of purity and the inorganic salts of titanium, the more high problems of production cost.
Summary of the invention
Above-mentioned deficiency to the prior art existence; It is simple to the purpose of this invention is to provide a kind of technology; Workable, low for equipment requirements, with low cost, and the effectively preparation method of the stabilized nano titanium dioxide suspension of degradation of organic substances of highlight catalytic active is arranged.
The technological means that the present invention solves the problems of the technologies described above is achieved in that
A kind of pair of presoma prepares the method for mixed crystal type nanometer titanium dioxide suspension, and its preparation process is:
(1) preparation TiCl
4Solution and TiCl
3Solution
Deionized water is cooled near 0 ℃, uses dry pipette to pipette a certain amount of TiCl
4, with dropping funel with TiCl
4In the deionized water that slowly joins ice-water bath and do not stop to stir, obtain water white TiCl
4Solution, final constant volume titanium ion concentration 0.5-1.0 mol/L, 0 ℃ of preservation is subsequent use;
Get a certain amount of TiCl
3, use the deionized water dissolved dilution, be mixed with the TiCl of concentration 0.5-1.0 mol/L
3Solution;
(2) the wet appearance of preparation nano titanium oxide
Get a certain amount of deionized water, add inorganic alkali solution and obtain the inorganic base deionized water solution, under condition of stirring, the TiCl for preparing in the step (1)
4Solution and TiCl
3Solution is according to Ti
4+: Ti
3+Join in the said inorganic base deionized water solution for the mixed of 9:1-1:5 and with mixed liquor; Up to the pH value of solution value is 1.0-2.5, and thermostatic crystallization 2-10h under 50-100 ℃ of condition obtains the white precipitate product; Through filtering, washing, obtain the wet appearance of nano titanium oxide;
(3) preparation of nano titanium dioxide suspension
The wet appearance of nano titanium oxide with step (2) makes adds the proper amount of deionized water dilution, and ultrasonic again dispersion 10-30 min promptly makes stable mixed crystal type nanometer titanium dioxide suspension.
Inorganic alkali solution in the said step (2) is ammoniacal liquor or NaOH or potassium hydroxide solution.
A preferred embodiment is: TiCl in the step (1)
4Solution and TiCl
3The concentration of solution is 0.5 mol/L; TiCl in the step (2)
4Solution and TiCl
3The mixed liquor of solution (Ti in the mixed liquor
4+: Ti
3+Be 4:1), be added drop-wise in the inorganic alkali solution with the speed of 1d/s, be to stop in 1.5 o'clock up to the pH value of solution value, at 95 ℃ of thermostatic crystallization 4 h.
Compare prior art, of the present invention have a following beneficial effect:
1. the present invention adopts the method for low-temperature hydrothermal crystallization to prepare nano titanium oxide, and the hard aggregation of both having avoided high-temperature calcination to bring has reduced requirement and energy consumption to production equipment again; And adopting cheap inorganic titanium salt is raw material, and the technology of this method is very simple, workable; Low for equipment requirements; Raw material is cheap, and product cost is low, is easy to realize large-scale industrial production.
2. the present invention adopts TiCl
4Solution and TiCl
3Drips of solution is added to the anti-phase dropping method of reacting in the alkali lye, makes that the particle diameter of the nano titanium oxide that reaction generates is littler, and photo-catalysis capability is stronger, and it is more stable to be mixed with suspension, can sedimentation.
3. the present invention without drying, and directly with a wet appearance preparation suspension, can reduce the nano titanium oxide that makes and prevent to reunite, and this suspension thin up does not need ultrasonicly just evenly to disperse again, and is easy to use.
4. the titanium dioxide that makes through this method has good degradation capability to organic pollution, and environmental improvement is had very big effect, can be used for aspects such as sewage, exhaust-gas treatment, and the automatically cleaning material is processed in the fields such as coating, weaving that can also be applied to.
The specific embodiment
The present invention is a raw material with titanium tetrachloride and titanium trichloride, through dissolved dilution, chemical precipitation reaction, control pH value, heating crystallization, filtration, washing, just makes the wet appearance of nano titanium oxide; Be raw material with the wet appearance of above-mentioned synthetic nano titanium oxide then, add a certain amount of deionized water, ultrasonic dispersion just makes the suspension of stabilized nano titanium dioxide.Concrete steps are following:
(1) preparation TiCl
4Solution and TiCl
3Solution
Deionized water is cooled near 0 ℃, uses dry pipette to pipette a certain amount of TiCl
4, with dropping funel slowly join ice-water bath and the deionized water that do not stop to stir in, obtain water white TiCl
4Solution, final constant volume titanium ion concentration 0.5-1.0 mol/L, 0 ℃ of preservation is subsequent use.Solvent deionized water is in ice-water bath, so press the TiCl of this method preparation
4Solution can hydrolysis.
Get a certain amount of TiCl
3, use the deionized water dissolved dilution, be mixed with the TiCl of concentration 0.5-1.0 mol/L
3Solution.
(2) the wet appearance of preparation nano titanium oxide
Get a certain amount of deionized water, add inorganic alkali solution (like the hydroxide solution of ammoniacal liquor or sodium or potassium) and obtain the inorganic base deionized water solution, under churned mechanically situation, the TiCl of preparation in the step (1)
4Solution and TiCl
3Solution makes Ti according to certain mixed
4+: Ti
3+=9:1-1:5 drips into certain speed, and regulator solution pH value stops to drip between the 1.0-2.5, at 50-100 ℃ of thermostatic crystallization 2-10h, obtains the white precipitate product, through filtering, washing, obtains the wet appearance of nano titanium oxide.
(3) preparation of nano titanium dioxide suspension
Wet appearance with making in the step (2) adds a certain amount of deionized water, and ultrasonic dispersion 10-30 min promptly makes the stabilized nano titanium dioxide suspension.The addition of deionized water should guarantee that the nano titanium oxide suspension has certain concentration, dilutes as required when being convenient to follow-up use, so as long as concentration is too not rare.
Experiment shows that the nano titanium oxide suspension that this method prepares has good degradation effect to organic matter.
Principle of the present invention: in alkaline solution, the titanium ion of different valence state directly generates deposition, the pH value of regulator solution, and the water-bath heating crystallization, thus realize having under the low temperature preparation of the nano titanium oxide of highlight catalytic active.
The embodiment that below provides a preparation explains.
(1) preparation TiCl
4Solution and TiCl
3Solution
Deionized water is cooled to about 0 ℃, uses dry pipette to pipette the TiCl of 54 ml
4(analyze pure, M=189.68, ρ=1.726 g/ml), with dropping funel slowly join ice-water bath and the deionized water that do not stop to stir in, obtain water white TiCl
4Solution, constant volume are processed the TiCl that concentration is 0.5 mol/L in the volumetric flask of 1000 ml
4Solution, 0 ℃ of preservation is subsequent use.
Get TiCl
3(analyze pure, M=156.26, ρ=1.192 g/ml, w=16-18%) 100 ml, dissolved dilution, constant volume process the TiCl that concentration is 0.5 mol/L in the volumetric flask of 250 ml
3Solution, subsequent use.
(2) the wet appearance of preparation mixed crystal type nanometer titanium dioxide
Get the deionized water of 100 ml, (analyze pure, M=35 w=25-28%), under churned mechanically situation, gets the TiCl of step (1) preparation to add 15 ml ammoniacal liquor
4Solution 80 ml and TiCl
3Solution 20 ml mix (Ti in the mixed liquor
4+: Ti
3+Be 4:1), drip into the speed of 1d/s, be to stop in 1.5 o'clock to the pH value of solution value, at 95 ℃ of insulation 4 h, obtain the white precipitate product, through filtering, washing is to the AgNO that in filtrating, drips 0.1 mol/L
3Solution does not have deposition and produces, and obtains the wet appearance of nano titanium oxide.Detect through XRD and to draw that anatase titanium dioxide and rutile titanium dioxide content are respectively 60.4% and 39.6% in the sample.
(3) preparation of nano titanium dioxide suspension
Wet appearance with making in the step (2) adds certain deionized water, and ultrasonic dispersion 20 min make the stabilized nanoscale titanium dioxide suspension.Recording solid content according to GB/T2793-1995 " mensuration of adhesive non-volatile content " is 2.11%.
Applying detection instance: get nano titanium oxide suspension 10.42 g and 3 mmol/L rhodamine B solution, 2.00 ml that prepare in the foregoing description; The preparation become the catalyst quality percentage composition be 0.1% with rhodamine B dyestuff quality percentage composition be aaerosol solution 200 g (getting ρ=1.0 g/ml) of 0.03 mmol/L; Using pipette to measure solution to 6 internal diameter is each 25 ml in the 7.5 cm culture dishes; Make sample path length be about 1 cm; One is not carried out the ultraviolet degraded, and remaining 5 culture dish places apart from low-pressure mercury fluorescent tube vertical range 10 cm places, whenever takes out a culture dish at a distance from 10 min; Measure the absorbance of rhodamine B with ultraviolet specrophotometer at 553 nm places, during 50 min in the solution 88.5% rhodamine B be degraded.And in whole process, suspension is in stable status always and does not precipitate generation.This description of test, the nano titanium oxide suspension of the present invention preparation is degradation of organic substances effectively, and this suspension is very stable sedimentation can not take place.
The above embodiment of the present invention only be for explanation the present invention did for example, and be not to be qualification to embodiment of the present invention.For the those of ordinary skill in affiliated field, can also make other multi-form variation and changes on the basis of the above description.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention amplifies out or change still are in protection scope of the present invention.
Claims (3)
1. two presomas prepare the method for mixed crystal type nanometer titanium dioxide suspension, and it is characterized in that: its preparation process is:
(1) preparation TiCl
4Solution and TiCl
3Solution
Deionized water is cooled near 0 ℃, uses dry pipette to pipette a certain amount of TiCl
4, with dropping funel with TiCl
4In the deionized water that slowly joins ice-water bath and do not stop to stir, obtain water white TiCl
4Solution, final constant volume titanium ion concentration 0.5-1.0 mol/L, 0 ℃ of preservation is subsequent use;
Get a certain amount of TiCl
3, use the deionized water dissolved dilution, be mixed with the TiCl of concentration 0.5-1.0 mol/L
3Solution;
(2) the wet appearance of preparation nano titanium oxide
Get a certain amount of deionized water, add inorganic alkali solution and obtain the inorganic base deionized water solution, under condition of stirring, the TiCl for preparing in the step (1)
4Solution and TiCl
3Solution is according to Ti
4+: Ti
3+Join in the said inorganic base deionized water solution for the mixed of 9:1-1:5 and with mixed liquor; Up to the pH value of solution value is 1.0-2.5, and thermostatic crystallization 2-10h under 50-100 ℃ of condition obtains the white precipitate product; Through filtering, washing, obtain the wet appearance of nano titanium oxide;
(3) preparation of nano titanium dioxide suspension
The wet appearance of nano titanium oxide with step (2) makes adds the proper amount of deionized water dilution, and ultrasonic again dispersion 10-30 min promptly makes stable mixed crystal type nanometer titanium dioxide suspension.
2. the method for preparing the mixed crystal type nanometer titanium dioxide suspension according to claim 1 is characterized in that: the inorganic alkali solution in the said step (2) is ammoniacal liquor or NaOH or potassium hydroxide solution.
3. the method for preparing the mixed crystal type nanometer titanium dioxide suspension according to claim 1 and 2 is characterized in that: TiCl in the said step (1)
4Solution and TiCl
3The concentration of solution is 0.5 mol/L; TiCl in the step (2)
4Solution and TiCl
3The mixed liquor of solution is added drop-wise in the inorganic base deionized water solution Ti in the mixed liquor with the speed of 1d/s
4+: Ti
3+Being 4:1, is to stop in 1.5 o'clock up to the pH value of solution value, at 95 ℃ of thermostatic crystallization 4 h.
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| CN103553124B (en) * | 2013-11-08 | 2015-03-11 | 中国科学技术大学 | Method for preparing blue titanium dioxide |
| CN105271400B (en) * | 2015-12-04 | 2017-06-30 | 华东理工大学 | A kind of preparation method of mixed crystal nano-titanium dioxide |
| CN108183141A (en) * | 2017-12-28 | 2018-06-19 | 成都中建材光电材料有限公司 | A kind of cadmium telluride thin-film battery of new structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814550A (en) * | 2006-03-03 | 2006-08-09 | 河北大学 | Method for preparing hano-level titanium dioxide by controlling crystal form |
| CN101306838A (en) * | 2008-07-01 | 2008-11-19 | 上海大学 | Method for preparing high- stable neutral mixed crystal nanometer TiO2 hydrosol |
| CN101318128A (en) * | 2008-07-23 | 2008-12-10 | 天津大学 | Method of preparing anatase structured highlight catalytic active nano-TiO2 |
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| CN101595059A (en) * | 2006-09-21 | 2009-12-02 | 托库森美国股份有限公司 | The temperature production method of the TiO 2 particles of nanometer size |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814550A (en) * | 2006-03-03 | 2006-08-09 | 河北大学 | Method for preparing hano-level titanium dioxide by controlling crystal form |
| CN101306838A (en) * | 2008-07-01 | 2008-11-19 | 上海大学 | Method for preparing high- stable neutral mixed crystal nanometer TiO2 hydrosol |
| CN101318128A (en) * | 2008-07-23 | 2008-12-10 | 天津大学 | Method of preparing anatase structured highlight catalytic active nano-TiO2 |
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