CN101580275A - Method for preparing titanium dioxide hollow spherical powder - Google Patents
Method for preparing titanium dioxide hollow spherical powder Download PDFInfo
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- CN101580275A CN101580275A CNA2008101067056A CN200810106705A CN101580275A CN 101580275 A CN101580275 A CN 101580275A CN A2008101067056 A CNA2008101067056 A CN A2008101067056A CN 200810106705 A CN200810106705 A CN 200810106705A CN 101580275 A CN101580275 A CN 101580275A
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- spherical powder
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Abstract
The invention discloses a method for preparing titanium dioxide hollow spherical powder, belonging to the technical field of material powder preparation. The method comprises the following steps: firstly, TiCl4 is added into ion liquid with a proper amount; the mixture is stirred uniformly with ultrasonic; deionized water is slowly added, wherein water is in the upper layer; after a period of time, water gradually enters an ion liquid layer to hydrolyze the TiCl4 to obtain a deposit ; because the obtained solution has lamination phenomenon, liquid at the upper layer is separated according to colors, and the ion liquid can be repeatedly utilized; and the deposit is washed by the deionized water and ethanol, separated by centrifugation, dried and baked to obtain the titanium dioxide hollow spherical powder with favorable dispersivity. The method has the advantages of simple and easily controlled process parameters, uniform and adjustable granularity, resource saving, little pollution, and the like.
Description
Technical field
The present invention relates to a kind of method for preparing the nano titanium oxide hollow spherical powder, belong to material science, relate in particular to the nano powder preparation technical field.
Technical background
Nano ceramics is to be the nano-scale (new ceramic material that the particles solidify of 1nm～100nm) forms by particle diameter.Its grain-size, pore size, defect size and grain boundary width etc. all should only limit to nanometer scale, have the special performance that is different from traditional ceramics.Wherein grain-size has very remarkable influence to ceramic performance, and the reducing of grain-size will make material get the raising that mechanical property has the order of magnitude, help improving toughness of material and plasticity simultaneously.Therefore the preparation of nano-powder becomes the basis of nano ceramics research.The granule-morphology of powder, globule size and distribution and purity thereof all are decided by its preparation method and technological process.Titanium dioxide since its have good electricity, optical property and have a wide range of applications at aspects such as photocatalyst material, gas sensor, secondary cells.
Though it is a lot of to prepare the method for titanium dioxide powder, as chemical coprecipitation, sol-gel method, hydropyrolysis process, reverse micelle method, hydrothermal synthesis method, chemical Vapor deposition process etc., wherein wet chemical method such as chemical coprecipitation simply is widely used because of technological process, but exist cause powder granularity size inequality and distribution broadening owing to precipitation process is wayward, the production cycle is long, energy consumption is big and shortcoming such as seriously polluted.
Summary of the invention
The objective of the invention is to propose a kind of method for preparing titanium dioxide hollow spherical powder, by TiCl in order to solve the shortcoming that prior art exists
4Be dissolved in the higher density solution of formation temperature in the ionic liquid, slowly add entry, TiCl on the solution upper strata
4Hydrolysis slowly takes place on the interface.This method has reduced the topsoil that ammoniacal liquor brings as reactant, ionic liquid can recycle and reuse, because the HCl that produces during hydrolysis provides strong acid environment for reaction, reduced the generation of coacervate, improved the dispersiveness of powder, also improved the purity of prepared powder simultaneously, be convenient to the later stage powder and cleaned, this method synthesis temperature is low, pollution-free, economize on resources.
The present invention proposes a kind of method for preparing titanium dioxide hollow spherical powder, it is characterized in that: by TiCl
4Be dissolved in the higher density solution of formation temperature in the ionic liquid, slowly add entry, TiCl on the solution upper strata
4Hydrolysis slowly takes place on the interface.Speed of reaction and product particle diameter can be by temperature and the controls of upper strata pH value of aqueous solution.The white precipitate that hydrolysis produces promptly gets the spherical powder of white titanium dioxide behind washing → drying → sieve → roast.Its processing step is as follows:
(1) with TiCl
4Be dissolved in the ionic liquid, forming concentration is the solution of 0.1M～1M;
(2) slowly add deionized water or weak base alkaline aqueous solution by certain volume ratio, the water or the aqueous solution are on the upper strata, and two kinds of liquid have tangible interface.
(3) after reaction for some time, gained solution divides three layers, is the colourless aqueous solution, colored ion liquor and white precipitate layer from top to bottom successively.Two-layer liquid is taken out respectively, and ionic liquid layer is waited until and is handled the back recycling.
(4) throw out is placed in the baking oven after washing, alcohol are washed (or acetonitrile extraction), filtration, in 325K～385K scope, and dry 3h～24h;
(5) will dry material and place silicon carbide rod furnace, be heated to furnace cooling behind 473K～773K insulation 1h～6h, promptly get white powder by the temperature rise rate of 1K/min～10K/min;
(6) gained white powder is not needed to grind fragmentation, promptly get the spherical powder of dispersed titanium dioxide preferably.
Ionic liquid described in the present invention comprises that density is greater than 1.1g/cm
3, fusing point is lower than the various glyoxaline ion liquids of 323K as [emim] [BF
4], [emim] [PF
6], [emim] [CF
3COO], [emim] [CF
3SO
3], [bmim] [BF
4], [bmim] [PF
6], [bmim] [CF
3COO], [bmim] [CF
38O
3] etc.
TiCl described in the present invention
4Ionic liquid solution concentration be 0.1M～1M.
The pH value of aqueous solution of upper strata described in the present invention is 1～9.
The temperature of surface reaction described in the present invention is 288K～385K.
TiCl described in the present invention
4Can use Ti (OBu)
4Replace Deng titanate or ester.
The products therefrom of reaction described in the present invention can be selected different treatment processs according to its purposes, as need high-purity Ti O
2, then the gained precipitation extracts with acetonitrile; As the adulterated TiO of need nonmetallic ion F
2Photocatalyst can directly be washed or alcohol is washed.
Ionic liquid described in the present invention can reuse, and the rate of recovery reaches more than 70%.
For the method for preparing titanium dioxide hollow spherical powder proposed by the invention, it is characterized in that: this reaction need not to stir, after gained precipitates centrifugal collection, sample after the electron microscopic observation treatment of different temperature, find that powder after drying is the hollow ball of 100nm～2000nm, ultimate analysis finds with having only titanium, two kinds of elements of oxygen to exist in the stripped sample of acetonitrile the impurity of contained element in the small amount of ionic liquid body to be arranged all in the sample that washing and alcohol are washed.TiO
2The existence of some nonmetallic impurity such as N, F can improve its response at visible light wave range as photocatalyst the time, so this method can be regulated and control its composition according to the different purposes of gained powder.
Outstanding feature of the present invention is:
(1) with TiCl
4Be dissolved in the ionic liquid, forming concentration is the solution of 0.1M～1M, slowly adds deionized water or weak base alkaline aqueous solution by certain volume ratio, and the water or the aqueous solution is on the upper strata, TiCl
4Hydrolysis takes place on liquid-liquid interface, and the size of gained spheroid is controlled by starting point concentration.
(2) reaction conditions is strong acidic environment (pH＜3), does not need strict control;
(3) the powder synthesis temperature is low, just forms at the room temperature nucleus;
(4) can adjust powder spherical diameter size and distribution by control reaction temperature and thermal treatment temp;
(5) gained powder composition can be regulated as required.
(6) the inventive method has advantages such as technological factor is simple and easy to control, environmental pollution is little.
Since ion liquid introducing, TiCl
4With ionic liquid bonding in a certain way, TiCl
4At the interface hydrolysis takes place, reaction belongs to diffusion control, because ionic liquid has less interfacial energy, and while TiCl
4Hydrolysis produces a large amount of HCl, makes hydrolysis environment be in strong acid condition, and the colloidal solid of generation is spherical from forming, and the surface has positive charge, has hindered the reunion of reaction product, finally obtains the high quality titanium dioxide nano-sphere body of good dispersity.Since ion liquid water-soluble better, therefore be easy to remove totally, obtain high-purity Ti O
2, also can make the certain non-metallic element of doping in the products therefrom as required.
According to method proposed by the invention, can under lower temperature, directly obtain titanium dioxide hollow spherical powder; The processing parameter variable range is wide; Energy consumption is low to economize on resources; The environmental pollution minor benefit is in environmental protection; The spherical powder purity of gained height, even particle size distribution, be convenient to industrial amplification production.
Description of drawings:
Fig. 1 is the technological process of preparation titanium dioxide hollow spherical powder;
Fig. 2 is embodiment 1 a gained nanometer ball scanning electron microscope picture;
Fig. 3 is embodiment 2 gained nanometer ball scanning electron microscope pictures;
Fig. 4 is embodiment 3 thus obtained microsphere scanning electron microscope pictures;
Fig. 5 is embodiment 4 gained nanometer ball scanning electron microscope pictures.
Concrete enforcement:
Below by embodiment specific implementation process is illustrated.
Embodiment 1
By mole concentration 0.1M preparation TiCl
41-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid solution, ultra-sonic dispersion forms brown-red solution; Measured 6ml TiCl in 2: 3 by volume respectively
4Solution and 9ml deionized water.Earlier the bigger TiCl of density
4Ionic liquid solution join in the 25ml sample bottle, slowly add deionized water again, between two kinds of liquid tangible interface is arranged.Temperature remains on 288K, produces white casse behind the 2h, and precipitation is gradually to ionic liquid layer infiltration, still layering of liquid after the sedimentation of 24h postprecipitation.Take out upper strata colourless solution and lower floor's light red solution respectively.Record upper solution pH value less than 1, lower floor's solution imidazole salts content is higher, records the pH value and is about 1.Lower floor's solution is waited until recycling.The white precipitate centrifugation is washed to AgNO
3Detect no Cl
-, last is washed all over alcohol, and afterwards that throw out is dry in baking oven, temperature is 325K, and soaking time 3 hours is carried out transmission electron microscope observing then.Analytical results shows that scanning electron microscopic observation shows that the gained sphere diameter is 100nm～200nm (Fig. 2), and the electron diffraction ring appears in the projection electronic microscope photos, and this shows that the titanium dioxide nucleus forms, so this method has the low characteristics of synthesis temperature.
Embodiment 2
By mole concentration 0.5M preparation TiCl
41-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid solution, ultra-sonic dispersion forms brown-red solution; Measured 9ml TiCl in 3: 2 by volume respectively
4Solution and 6ml deionized water.Earlier the bigger TiCl of density
4Ionic liquid solution join in the 25ml sample bottle, slowly add deionized water again, between two kinds of liquid tangible interface is arranged.Temperature remains on 288K, produces white casse behind the 2h, and to the ionic liquid layer infiltration, the 34h posthydrolysis is complete gradually for precipitation, takes out upper strata colourless solution and lower floor's light red solution respectively after the precipitation sedimentation, and lower floor's solution is waited until recycling.The white precipitate centrifugation is washed to AgNO
3Detect no Cl
-, last is washed all over alcohol, and afterwards that throw out is dry in baking oven, temperature is 325K, and soaking time 3 hours is carried out scanning electron microscopic observation then.Analytical results shows that sphere diameter evenly is 400nm～500nm (accompanying drawing 3).
Embodiment 3
By mole concentration 1.0M preparation TiCl
41-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid solution, ultra-sonic dispersion forms brown-red solution; Measured 9ml TiCl in 3: 2 by volume respectively
4Solution and 6ml deionized water.Earlier the bigger TiCl of density
4Ionic liquid solution join in the 25ml sample bottle, slowly add deionized water again, between two kinds of liquid tangible interface is arranged.Temperature remains on 288K, and the 46h posthydrolysis is complete, takes out upper strata colourless solution and lower floor's light red solution respectively after the precipitation sedimentation, and lower floor's solution is waited until recycling.The white precipitate centrifugation is washed to AgNO
3Detect no Cl
-, last is washed all over alcohol, and afterwards that throw out is dry in baking oven, temperature is 325K, and soaking time 3 hours is carried out scanning electron microscopic observation then.Analytical results shows that sphere diameter evenly is 1 μ m～2 μ m (accompanying drawing 4).
Embodiment 4
By mole concentration 0.5M preparation TiCl
41-butyl-3-Methylimidazole hexafluorophosphate ionic liquid solution, ultra-sonic dispersion forms brown-red solution; Measured 9ml TiCl in 3: 2 by volume respectively
4Solution and 6ml deionized water.Earlier the bigger TiCl of density
4Ionic liquid solution join in the 25ml sample bottle, slowly add deionized water again, between two kinds of liquid tangible interface is arranged.Temperature remains on 293K, and the 36h posthydrolysis is complete, takes out upper strata colourless solution and lower floor's light red solution respectively after the precipitation sedimentation, and lower floor's solution is waited until recycling.The white precipitate centrifugation is washed to AgNO
3Detect no Cl
-, last is washed all over alcohol, and afterwards that throw out is dry in baking oven, temperature is 325K, and soaking time 3 hours is carried out scanning electron microscopic observation then.Analytical results shows that sphere diameter evenly is 500nm～600nm (accompanying drawing 5).
Embodiment 5
By mole concentration 0.5M preparation TiCl
41-butyl-3-Methylimidazole hexafluorophosphate ionic liquid solution, ultra-sonic dispersion forms brown-red solution; Measured 9ml TiCl in 3: 2 by volume respectively
4Solution and 6ml deionized water.Earlier the bigger TiCl of density
4Ionic liquid solution join in the 25ml sample bottle, slowly add deionized water again, between two kinds of liquid tangible interface is arranged.Temperature remains on 303K, and the 30h posthydrolysis is complete, takes out upper strata colourless solution and lower floor's light red solution respectively after the precipitation sedimentation, and lower floor's solution is waited until recycling.The white precipitate centrifugation is washed to AgNO
3Detect no Cl
-, last is washed all over alcohol, and afterwards that throw out is dry in baking oven, temperature is 325K, and soaking time 3 hours is carried out scanning electron microscopic observation then.Analytical results shows that sphere diameter evenly is 300nm～400nm.
Embodiment 6
By mole concentration 0.5M preparation TiCl
41-butyl-3-Methylimidazole hexafluorophosphate ionic liquid solution, ultra-sonic dispersion forms brown-red solution; Measured 9ml TiCl in 3: 2 by volume respectively
4Solution and 6ml deionized water.Earlier the bigger TiCl of density
4Ionic liquid solution join in the 25ml sample bottle, slowly add deionized water again, between two kinds of liquid tangible interface is arranged.Temperature remains on 323K, and the 20h posthydrolysis is complete, takes out upper strata colourless solution and lower floor's light red solution respectively after the precipitation sedimentation, and lower floor's solution is waited until recycling.The white precipitate centrifugation is washed to AgNO
3Detect no Cl
-, last is washed all over alcohol, and afterwards that throw out is dry in baking oven, temperature is 325K, and soaking time 3 hours is carried out scanning electron microscopic observation then.Analytical results shows that sphere diameter evenly is 200nm～300nm.
Embodiment 7
By mole concentration 0.5M preparation TiCl
41-butyl-3-Methylimidazole hexafluorophosphate ionic liquid solution, ultra-sonic dispersion forms brown-red solution; Measured 9ml TiCl in 3: 2 by volume respectively
4Solution and 6ml pH value are 9 NaAc solution.Earlier the bigger TiCl of density
4Ionic liquid solution join in the 25ml sample bottle, slowly add the pH value again and be 9 NaAc solution, between two kinds of liquid tangible interface is arranged.Temperature remains on 303K, and the 24h posthydrolysis is complete, takes out upper strata colourless solution and lower floor's light red solution respectively after the precipitation sedimentation, and lower floor's solution is waited until recycling.The white precipitate centrifugation is washed to AgNO
3Detect no Cl
-, last is washed all over alcohol, and afterwards that throw out is dry in baking oven, temperature is 325K, and soaking time 3 hours is carried out scanning electron microscopic observation then.Analytical results shows that sphere diameter evenly is 300nm～400nm.
As can be seen from the above embodiments, by surface reaction, can obtain nano-hollow spheroid uniformly according to the particle diameter of speed of response better controlled gained nanometer (little) ball.PH value to aqueous layer has no particular limits simultaneously.Therefore have characteristics such as simple to operate, that preparation cycle is controlled, be convenient to enlarge scale production.
According to method proposed by the invention, can prepare high-quality titanium dioxide hollow spherical powder, and can industrial amplification production.
Claims (8)
1. method for preparing the nano titanium oxide hollow spherical powder, it is characterized in that: this method is TiCl
4Ionic liquid solution and deionized water TiCl takes place on liquid-liquid interface
4Hydrolysis, the reaction conditions gentleness need not heat, the gained hydrolysate through washing, dry, sieve, behind the roast, promptly get white titanium dioxide hollow spherical powder, its processing step is as follows:
(1) at first with TiCl
4Be dissolved in the ionic liquid, form homogeneous, stable, transparent colored solutions;
(2) slowly add deionized water or weak base alkaline aqueous solution by certain volume ratio, the water or the aqueous solution are on the upper strata, and two kinds of liquid have tangible interface;
(3) after reaction for some time, gained solution divides three layers, is the colourless aqueous solution, colored ion liquor and white precipitate layer from top to bottom successively, and two-layer liquid is taken out respectively, and ionic liquid layer is waited until and handled the back recycling;
(4) throw out is placed in the baking oven after washing, alcohol are washed (or acetonitrile extraction), filtration, in 325K～385K scope, and dry 3h～24h;
(5) will dry material and place silicon carbide rod furnace, be heated to furnace cooling behind 473K～773K insulation 1h～6h, promptly get white powder by the temperature rise rate of 1K/min～10K/min;
(6) gained white powder is not needed to grind fragmentation, promptly get dispersed titanium dioxide hollow spherical powder preferably.
2. according to the described method for preparing titanium dioxide hollow spherical powder of claim 1, it is characterized in that: ionic liquid comprises density greater than 1.1, and fusing point is lower than the various glyoxaline ion liquids of 323K as [emim] [BF
4], [emim] [PF
6], [emim] [CF
3COO], [emim] [CF
3SO
3], [bmim] [BF
4], [bmim] [PF
6], [bmim] [CF
3COO], [bmim] [CF
3SO
3] etc.
3. according to the described method for preparing titanium dioxide hollow spherical powder of claim 1, it is characterized in that: TiCl
4Ionic liquid solution in, TiCl
4Concentration be 0.1M～1M.
4. according to the described method for preparing titanium dioxide hollow spherical powder of claim 1, it is characterized in that: the upper strata pH value of aqueous solution is 1～9.
5. according to the described method for preparing titanium dioxide hollow spherical powder of claim 1, it is characterized in that: the temperature of surface reaction is 288K～385K.
6. according to the described method for preparing titanium dioxide hollow spherical powder of claim 1, it is characterized in that: as the TiCl in titanium source
4Can use Ti (OBu)
4Replace in facile hydrolysis titanium source.
7. according to the described method for preparing titanium dioxide hollow spherical powder of claim 1, it is characterized in that: the reaction products therefrom can be selected different treatment processs according to its purposes, as need high-purity Ti O
2, then the gained precipitation extracts with acetonitrile; As the adulterated TiO of need nonmetallic ion F
2Photocatalyst can directly be washed or alcohol is washed.
8. according to the described method for preparing titanium dioxide hollow spherical powder of claim 1, it is characterized in that: the ionic liquid that reacts used can reuse, and the rate of recovery reaches more than 70%.
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| CN107376884A (en) * | 2017-07-17 | 2017-11-24 | 奥为（天津）环保科技有限公司 | A kind of Ti with hollow-core construction3+/TiO2The preparation method of photochemical catalyst |
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