CN103818953A - Method for preparing micro-nano-TiO2 spherical particles and prepared spherical particles - Google Patents
Method for preparing micro-nano-TiO2 spherical particles and prepared spherical particles Download PDFInfo
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- CN103818953A CN103818953A CN201410041105.1A CN201410041105A CN103818953A CN 103818953 A CN103818953 A CN 103818953A CN 201410041105 A CN201410041105 A CN 201410041105A CN 103818953 A CN103818953 A CN 103818953A
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- 238000000034 method Methods 0.000 title claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000012798 spherical particle Substances 0.000 title abstract 6
- 239000002245 particle Substances 0.000 claims abstract description 68
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- -1 titanium ester Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 11
- 229960004756 ethanol Drugs 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000004108 freeze drying Methods 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 40
- 239000000839 emulsion Substances 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- RHXHGRAEPCAFML-UHFFFAOYSA-N 7-cyclopentyl-n,n-dimethyl-2-[(5-piperazin-1-ylpyridin-2-yl)amino]pyrrolo[2,3-d]pyrimidine-6-carboxamide Chemical compound N1=C2N(C3CCCC3)C(C(=O)N(C)C)=CC2=CN=C1NC(N=C1)=CC=C1N1CCNCC1 RHXHGRAEPCAFML-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000005502 phase rule Effects 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention relates to a method for preparing micro-nano-TiO2 spherical particles and prepared spherical particles. The method comprises the following steps: adding heptanoic acid into anhydrous ethanol, uniformly mixing, and adding titanium ester; stirring for 0.5-2 hours at 10-50 DEG C; adding water, and continuously stirring for 1-3 hours; separating to obtain a precipitate, washing the precipitate, and freeze-drying the precipitate; calcining the precipitate at 300-700 DEG C to obtain the micro-nano-TiO2 spherical particles. The micro-nano-TiO2 spherical particles prepared by the method are uniform in particle size distribution, regular in morphology, high in degree of crystallinity, high in dispersion and high in product purity; the preparation method is easy in operation, environment-friendly, mild in reaction conditions, low in energy consumption and easy to popularize.
Description
Technical field
The present invention relates to conductor oxidate material technology field, relate in particular to one and prepare micro-nano TiO
2the method of spheroidal particle and the spheroidal particle making.
Background technology
Titanium dioxide (TiO
2) as a kind of important conductor oxidate, since the sixties in last century, be widely used in the fields such as pigment, coating, ink, makeup and environmental pollution improvement with its excellent physical and chemical performance.Particularly its excellent photochemical catalysis and photoelectric properties, make TiO
2in the new industry such as photochemical catalysis and solar cell, also obtain a large amount of application.TiO
2these application have close contacting with himself pattern, size, crystalline structure etc.TiO
2common crystal formation has three kinds: brookite, anatase octahedrite and rutile, wherein anatase octahedrite TiO
2show excellent performance at the aspect such as photochemical catalysis and solar cell.In recent years, monodisperse spherical TiO
2particle has attracted numerous investigators' concern.This is because have the micro-nano spherical TiO of size distribution homogeneous
2particle, is with a wide range of applications in high-tech areas such as high-performance ceramic, catalyzer, photonic crystals.Meanwhile, it has very important application in metering and field fo standardization.Therefore, the micro-nano TiO of the anatase crystal of prepared sizes homogeneous
2spheroidal particle has great importance.
At present, micro-nano TiO
2the preparation method of material has vapor phase process and liquid phase method.Wherein vapor phase process is because energy consumption is large, cost is high and the reason use range such as complex process is less, and liquid phase rule is due to energy consumption and cost is relatively low, good uniformity and required equipment is simple etc. that advantage is widely used.Conventional in liquid phase method have the hot method of chemical precipitation method, hydrolysis method, sol-gel method and water/alcohol and a microemulsion method etc.Wherein, hydrolysis method is a kind of common method.Utilize the uniform spherical TiO of metal alkoxide hydrolysis prepared sizes
2particle, method is simple, and product purity is high, but TiO
2presoma hydrolysis rate is very fast, causes final product distribution of sizes wider, and monodispersity is poor.
Summary of the invention
For the defect of prior art, the object of the present invention is to provide one to prepare micro-nano TiO
2the method of spheroidal particle and the spheroidal particle making, the micro-nano TiO that described method utilizes the auxiliary hydrolysis method of enanthic acid to make
2spheroidal particle size-grade distribution homogeneous.
For realizing object of the present invention, by the following technical solutions:
In first aspect, the invention provides one and prepare micro-nano TiO
2the method of spheroidal particle, comprising: enanthic acid is added in dehydrated alcohol, after mixing, add titanic acid ester; 10～50 ℃ are stirred 0.5-2 hour; Add water, continue to stir 1-3 hour; Separation is precipitated thing, washs described throw out lyophilize; Finally, in 300～700 ℃ of calcinings, obtain micro-nano TiO
2spheroidal particle.
As the preferred technical solution of the present invention, described method comprises the steps:
(1) enanthic acid of 0.1～1.0 parts by volume is added in the dehydrated alcohol of 100 parts by volume, after mixing, then add the titanic acid ester of 0.1～5.0 parts by volume;
(2) system step (1) being obtained stirs 0.5-2 hour in 10～50 ℃;
(3) in the system obtaining to step (2), add 5～50 parts by volume water, continue to stir 1-3 hour;
(4) system step (3) being obtained separates and is precipitated thing, washs described throw out lyophilize;
(5) by step (4) products therefrom in 300～700 ℃ of calcinings, obtain micro-nano TiO
2spheroidal particle.
In the present invention, in described step (1), the molecular formula of titanic acid ester can be Ti (OR)
4, wherein R is-C
nh
2n+1, the integer of n=2～4, described titanic acid ester can be titanium ethanolate, isopropyl titanate or butyl (tetra) titanate etc.Wherein, titanium ethanolate claims again tetraethyl titanate, and molecular formula is Ti (OCH
2cH
3)
4, structural formula is
isopropyl titanate claims again titanium isopropylate, and molecular formula is (CH
3cH
3cHO)
4ti, structural formula is
butyl (tetra) titanate claims again tetra-n-butyl titanate, and molecular formula is (CH
3cH
2cH
2cH
2o)
4ti, structural formula is
preferably, described titanic acid ester is butyl (tetra) titanate.
In the present invention, in described step (1), with respect to the dehydrated alcohol of 100 parts by volume, the add-on of enanthic acid can be 0.1 parts by volume, 0.12 parts by volume, 0.15 parts by volume, 0.2 parts by volume, 0.4 parts by volume, 0.6 parts by volume, 0.9 parts by volume, 0.95 parts by volume, 0.98 parts by volume or 0.99 parts by volume; Preferably, the add-on of described enanthic acid is 0.2～0.6 parts by volume.
In the present invention, in described step (1), with respect to the dehydrated alcohol of 100 parts by volume, the add-on of titanic acid ester can be 0.2 parts by volume, 0.3 parts by volume, 0.5 parts by volume, 0.8 parts by volume, 1 parts by volume, 2 parts by volume, 3 parts by volume, 4 parts by volume, 4.5 parts by volume or 4.8 parts by volume; Preferably, the add-on of described titanic acid ester is 0.5～2.0 parts by volume.
In the present invention, in described step (2), temperature of reaction can be 12 ℃, 14 ℃, 15 ℃, 20 ℃, 28 ℃, 33 ℃, 40 ℃, 46 ℃ or 49 ℃; Preferably, described step (2) temperature of reaction is 20～40 ℃.
In the present invention, in described step (2), churning time can be 0.55 hour, 0.6 hour, 0.7 hour, 0.8 hour, 1.2 hours, 1.5 hours, 1.8 hours, 1.9 hours or 1.95 hours; Preferably, described churning time is 1 hour.
In the present invention, in described step (3), with respect to the dehydrated alcohol of 100 parts by volume, the add-on of water can be 5.2 parts by volume, 6 parts by volume, 7 parts by volume, 10 parts by volume, 20 parts by volume, 30 parts by volume, 38 parts by volume, 42 parts by volume, 47 parts by volume or 49 parts by volume; Preferably, the add-on of described water is 10～40 parts by volume.Wherein, water can be deionized water or distilled water etc., preferably deionized water.
In the present invention, in described step (3), churning time can be 1.1 hours, 1.2 hours, 1.5 hours, 1.8 hours, 2.1 hours, 2.3 hours, 2.5 hours, 2.7 hours, 2.9 hours or 2.95 hours; Preferably, described churning time is 2 hours.
In the present invention, after described step (3) reaction, obtain white emulsion, then can be by the method sediment separate outs such as centrifugal or filtration, the preferred centrifugation of the present invention;
In the present invention, can be with throw out described in ethanol and/or deionized water wash in described step (4).
In the present invention, in described step (4), cryodesiccated temperature can be-75～-40 ℃, for example-74 ℃ ,-70 ℃ ,-65 ℃ ,-62 ℃ ,-58 ℃ ,-50 ℃ ,-45 ℃ ,-42 ℃ or-40 ℃.
In the present invention, in described step (5), the temperature of calcining can be 310 ℃, 320 ℃, 350 ℃, 380 ℃, 420 ℃, 500 ℃, 600 ℃, 650 ℃ or 680 ℃; Preferably, in described step (5), calcining temperature is 350～650 ℃.
In the present invention, so-called " parts by volume " only for representing the volume ratio relation between different components, and its unit can be milliliter (mL) or rise (L), for example can 10mL, 50mL, 100mL or 300mL etc. are 1 parts by volume, and its scope can be 10～500mL.
In second aspect, the invention provides a kind of micro-nano TiO preparing according to aforesaid method
2spheroidal particle, the median size 80-300 nanometer of described spheroidal particle, relative standard deviation is less than 6%.
Compared with prior art, beneficial effect of the present invention is as follows: the micro-nano TiO that adopts method of the present invention to obtain
2the grain good sphericity of spheroidal particle, pattern rule, better crystallinity degree, size are evenly, good dispersity, product purity be high, and described preparation method is simple to operate, environmental friendliness, and reaction conditions gentleness, energy consumption are low, are easy to promote the use of.
Accompanying drawing explanation
Fig. 1 is the micro-nano TiO that the embodiment of the present invention 1 makes
2the scanning electron microscope (SEM) photograph of spheroidal particle.
Fig. 2 is the micro-nano TiO that the embodiment of the present invention 1 makes
2the transmission electron microscope picture of spheroidal particle.
Fig. 3 is the micro-nano TiO that the embodiment of the present invention 2 makes
2the scanning electron microscope (SEM) photograph of spheroidal particle.
Fig. 4 is the micro-nano TiO that the embodiment of the present invention 2 makes
2the transmission electron microscope picture of spheroidal particle.
Fig. 5 is the micro-nano TiO that the embodiment of the present invention 1 and embodiment 2 make
2the XRD figure of spheroidal particle.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail.It will be understood to those of skill in the art that following examples are only the preferred embodiments of the present invention, so that understand better the present invention, thereby should not be considered as limiting scope of the present invention.For a person skilled in the art, the present invention can have various modifications and variations, within the spirit and principles in the present invention all, any modification of doing, is equal to and replaces or improvement etc., within all should being included in protection scope of the present invention.
Experimental technique in following embodiment, if no special instructions, is ordinary method; Experiment material used, if no special instructions, is and is purchased available from routine biochemistry chemical reagent work.
Micro-nano TiO in following embodiment
2the median size of spheroidal particle and relative standard deviation are by spheroidal particle in scanning electron microscope (SEM) photograph is measured in a large number, and obtain by a large amount of statistics of software ipwin32.
Embodiment 1
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 0.2mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 0.5mL butyl (tetra) titanate;
(2) system of step (1) is placed in to 28 ℃ of water-bath electric stirring constant temperature 1 hour;
(3) in step (2) system, drip 40mL deionized water, continue electric stirring 2 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-65 ℃ of lyophilizes of washing precipitate, 400 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the scanning electron microscope (SEM) photograph of spheroidal particle as shown in Figure 1, transmission electron microscope picture as shown in Figure 2, XRD figure as shown in Figure 5, visible described micro-nano TiO
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 100nm, relative standard deviation is 5%.
Embodiment 2
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 0.5mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 0.7mL butyl (tetra) titanate;
(2) system of step (1) is placed in to 28 ℃ of water-bath electric stirring constant temperature 1 hour;
(3) in step (2) system, drip 20mL deionized water, continue electric stirring 2 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-75 ℃ of lyophilizes of washing precipitate, 500 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the scanning electron microscope (SEM) photograph of spheroidal particle as shown in Figure 3, transmission electron microscope picture as shown in Figure 4, XRD figure as shown in Figure 5, visible described micro-nano TiO
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 200nm, relative standard deviation is 4%.
Embodiment 3
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 0.2mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 1.5mL butyl (tetra) titanate;
(2) system of step (1) is placed in to 26 ℃ of water-bath electric stirring constant temperature 1 hour;
(3) in step (2) system, drip 35mL deionized water, continue electric stirring 2 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-65 ℃ of lyophilizes of washing precipitate, 400 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 110nm, relative standard deviation is 5%.
Embodiment 4
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 0.2mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 0.8mL butyl (tetra) titanate;
(2) system of step (1) is placed in to 32 ℃ of water-bath electric stirring constant temperature 1 hour;
(3) in step (2) system, drip 20mL deionized water, continue electric stirring 2 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-50 ℃ of lyophilizes of washing precipitate, 400 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 82nm, relative standard deviation is 5%.
Embodiment 5
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 0.2mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 0.7mL butyl (tetra) titanate;
(2) system of step (1) is placed in to 22 ℃ of water-bath electric stirring constant temperature 1 hour;
(3) in step (2) system, drip 10mL deionized water, continue electric stirring 2 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-75 ℃ of lyophilizes of washing precipitate, 400 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 250nm, relative standard deviation is 4%.
Embodiment 6
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 0.1mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 0.1mL butyl (tetra) titanate;
(2) system of step (1) is placed in to 10 ℃ of water-bath electric stirring constant temperature 2 hours;
(3) in step (2) system, drip 5mL deionized water, continue electric stirring 3 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-40 ℃ of lyophilizes of washing precipitate, 700 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 120nm, relative standard deviation is 5%.
Embodiment 7
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 1mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 5mL butyl (tetra) titanate;
(2) system of step (1) is placed in to 50 ℃ of water-bath electric stirring constant temperature 0.5 hour;
(3) in step (2) system, drip 50mL deionized water, continue electric stirring 1 hour;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-75 ℃ of lyophilizes of washing precipitate, 300 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 180nm, relative standard deviation is 4%.
Embodiment 8
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 0.6mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 2mL titanium ethanolate;
(2) system of step (1) is placed in to 40 ℃ of water-bath electric stirring constant temperature 0.8 hour;
(3) in step (2) system, drip 40mL deionized water, continue electric stirring 2 hours;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-65 ℃ of lyophilizes of washing precipitate, 650 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 90nm, relative standard deviation is 5%.
Embodiment 9
The present embodiment is prepared micro-nano TiO by following steps
2spheroidal particle:
(1) enanthic acid of 0.2mL is added drop-wise in 100mL dehydrated alcohol, after mixing, then drips 0.5mL isopropyl titanate;
(2) system of step (1) is placed in to 20 ℃ of water-bath electric stirring constant temperature 2 hours;
(3) in step (2) system, drip 28mL deionized water, continue electric stirring 1 hour;
(4) after completion of the reaction, by the white emulsion centrifugation obtaining, also-40 ℃ of lyophilizes of washing precipitate, 350 ℃ of calcinings, obtain the micro-nano TiO of Detitanium-ore-type of size-grade distribution homogeneous
2spheroidal particle.
The prepared micro-nano TiO of the present embodiment
2the nano particle that spheroidal particle comprises a large amount of good sphericity, pattern rule, size uniform, good dispersity, the median size of particle is 220nm, relative standard deviation is 4%.
Applicant's statement, the present invention illustrates detailed features of the present invention and detailed method by above-described embodiment, but the present invention is not limited to above-mentioned detailed features and detailed method, do not mean that the present invention must rely on above-mentioned detailed features and detailed method could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention is selected the selection of the equivalence replacement of component and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope to the present invention.
Claims (10)
1. prepare micro-nano TiO for one kind
2the method of spheroidal particle, comprising: enanthic acid is added in dehydrated alcohol, after mixing, add titanic acid ester; 10～50 ℃ are stirred 0.5-2 hour; Add water, continue to stir 1-3 hour; Separation is precipitated thing, washs described throw out lyophilize; Finally, in 300～700 ℃ of calcinings, obtain micro-nano TiO
2spheroidal particle.
2. method according to claim 1, is characterized in that, described method comprises the steps:
(1) enanthic acid of 0.1～1.0 parts by volume is added in the dehydrated alcohol of 100 parts by volume, after mixing, then add the titanic acid ester of 0.1～5.0 parts by volume;
(2) system step (1) being obtained stirs 0.5-2 hour in 10～50 ℃;
(3) in the system obtaining to step (2), add 5～50 parts by volume water, continue to stir 1-3 hour;
(4) system step (3) being obtained separates and is precipitated thing, washs described throw out lyophilize;
(5) by step (4) products therefrom in 300～700 ℃ of calcinings, obtain micro-nano TiO
2spheroidal particle.
3. method according to claim 2, is characterized in that, in described step (1), the molecular formula of titanic acid ester is Ti (OR)
4, wherein R is-C
nh
2n+1, the integer of n=2～4, preferably, described titanic acid ester is butyl (tetra) titanate.
4. according to the method in claim 2 or 3, it is characterized in that, the add-on of described enanthic acid is 0.2～0.6 parts by volume.
5. according to the method described in claim 2-4 any one, it is characterized in that, the add-on of described titanic acid ester is 0.5～2.0 parts by volume.
6. according to the method described in claim 2-5 any one, it is characterized in that, described step (2) temperature of reaction is 20～40 ℃;
Preferably, described churning time is 1 hour.
7. according to the method described in claim 2-6 any one, it is characterized in that, in described step (3), the add-on of water is 10～40 parts by volume;
Preferably, described churning time is 2 hours.
8. according to the method described in claim 2-7 any one, it is characterized in that, in described step (4) by centrifugation throw out;
Preferably, with throw out described in ethanol and/or deionized water wash;
Preferably, described cryodesiccated temperature is-75～-40 ℃.
9. according to the method described in claim 2-8 any one, it is characterized in that, in described step (5), calcining temperature is 350～650 ℃.
10. a micro-nano TiO who prepares according to the method described in claim 1-9 any one
2spheroidal particle, is characterized in that, the median size 80-300 nanometer of described spheroidal particle, and relative standard deviation is less than 6%.
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| CN104211112A (en) * | 2014-09-05 | 2014-12-17 | 国家纳米科学中心 | Epigranular micro/nano TiO2 spherical particle, and preparation method and application thereof |
| CN110668494A (en) * | 2019-10-29 | 2020-01-10 | 北京工业大学 | High yield of pure anatase TiO2Simple synthesis of nanoparticles |
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