CN105417578A - Preparation method of cauliflower-shaped brookite type titanium dioxide - Google Patents
Preparation method of cauliflower-shaped brookite type titanium dioxide Download PDFInfo
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- CN105417578A CN105417578A CN201510874530.3A CN201510874530A CN105417578A CN 105417578 A CN105417578 A CN 105417578A CN 201510874530 A CN201510874530 A CN 201510874530A CN 105417578 A CN105417578 A CN 105417578A
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- titanium dioxide
- brookite type
- type titanium
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 35
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 17
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 claims description 49
- 240000003259 Brassica oleracea var. botrytis Species 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- -1 small molecule organic compound Chemical class 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of new energy materials, and in particular relates to a cauliflower-shaped brookite type titanium dioxide material and a preparation method thereof. The preparation method comprises the following steps: (A) preparing a titanium dioxide material by adopting a hydro-thermal method: adding a titanium precursor solution to an ammonia water and sodium borohydride solution under a stirring condition, and carrying out hydro-thermal reaction at 220-280 DEG C for 12-36h to obtain titanium dioxide precipitate; (B) washing; and (C) carrying out vacuum drying to obtain the cauliflower-shaped brookite type titanium dioxide material. The preparation method has the advantages that the preparation process is simple, the conditions are easy to control and the posttreatment is convenient, and is suitable for large-scale preparation of the cauliflower-shaped brookite type titanium dioxide material; and the cauliflower-shaped brookite type titanium dioxide material has important application in environment science and new energy fields.
Description
Technical field
The present invention relates to novel energy resource material technology field, specifically, is a kind of preparation method of cauliflower form brookite type titanium dioxide.
Background technology
From Fujishima and Honda in 1972 deliver on Nature magazine about TiO
2since the paper of water electrolysis hydrogen production, TiO
2large quantifier elimination has been carried out as catalyzer.From crystallography angle analysis, TiO
2for polymorphism, common crystalline phase is Rutile Type, Anatase and brookite.In recent years, the TiO of extensive self-assembly micron and nanostructure
2material causes people's extensive concern, but prepares brookite type TiO
2report less (Altomare, M, HighactivityofbrookiteTiO
2nanoparticlesinthephotocatalyticabatementofammoniainwate r.CatalysisToday.2015.252.184-189; Min-HanYang, AnataseandbrookiteTiO
2withvariousmorphologiesandtheirproposedbuildingblock.Cry stEngComm.2014.16.441-447).
Brookite type TiO
2pattern mainly contain flake, bar-shaped, flower-shaped these are several.But brookite type TiO
2building-up process in usually can with Detitanium-ore-type and rutile-type, pure brookite type TiO
2more difficult synthesis.Cauliflower form brookite type TiO
2specific surface area is large, and have more molecule or atomic contacts in the same time thus react, speed of response is faster.This cauliflower form brookite type titanium dioxide pattern also belongs to petal-shaped.Brookite type TiO
2main Application Areas is as photocatalyst, be used for degrade small molecule organic compound.
Chinese patent literature CN101880057A discloses a kind of preparation method of high pure brookite type titanium dioxide of morphology controllable, specifically: under whipped state, in certain density titanium sulfate solution, drip a certain amount of anhydrous sodium acetate, and then drip pH to 8 ~ 12 scope that sodium hydroxide solution makes suspension system; Then by above-mentioned reaction gained suspension presoma in water heating kettle through 160 DEG C ~ 300 DEG C hydro-thermal reactions 4 ~ 6 days, take out, washing, dry, obtain product.By controlling the pH value of reaction system, the temperature of hydro-thermal reaction, can prepare petal-shaped, shuttle shape and nanotube-shaped brookite type titanium dioxide.
Chinese patent literature CN103848457A discloses nitrogen-doped anatase crystal form titanium dioxide nano-powder and preparation method thereof, the method powder used is the anatase crystal nano TiO 2 powder doped with nitrogen, atomic percent between nitrogen wherein and anatase crystal titanium dioxide is 1.4 ~ 2.0at%:98.0 ~ 98.6at%, morphology microstructure is shuttle shape or bar-shaped, and precursor solution used is add ammoniacal liquor and hydrogen peroxide in the titanium nitride aqueous solution.
Chinese patent literature CN103771505A discloses a kind of synthetic method of titanium dioxide self-assembly particle, and the method take water as solvent, with TiCl
4or Organic Alcohol oxygen titanium is as titania precursor body, and add alkyl ammonium hydroxide as protective material, adopt hydrothermal method to synthesize cauliflower form and bar-shaped Titanium dioxide nanoparticle.Disclosed " cauliflower form " presoma used of this patent is TiCl
4but occur in preparation process that part cauliflower form part is bar-shaped, repeatability is bad.
But simple about a kind of technique, preparation cycle is short, and temperature of reaction is low, and the preparation method of the brookite type titanium dioxide of the cauliflower form pattern of favorable repeatability yet there are no report.
Summary of the invention
The object of the invention is for deficiency of the prior art, provide a kind of preparation cycle short, temperature of reaction is low, the preparation method of the cauliflower form brookite type titanium dioxide of favorable repeatability.
Second object of the present invention is, provides a kind of cauliflower form brookite type titanium dioxide material.
For achieving the above object, the technical scheme that the present invention takes is: a kind of preparation method of cauliflower form brookite type titanium dioxide, comprise the following steps: (A) adopts hydrothermal method to prepare titanic oxide material: under agitation condition, titanium source precursor solution is added ammoniacal liquor and sodium borohydride solution, at 220 ~ 280 DEG C, hydro-thermal reaction 12 ~ 36 hours, obtains titanium dioxide precipitation; (B) wash; (C) vacuum-drying, obtains cauliflower form brookite type titanium dioxide material.
Titanium source of the present invention presoma is titanous chloride.At titanous chloride, titanium tetrachloride, in this several presoma of tetrabutyl titanate, the product structure selecting titanous chloride to obtain is best, and repeatability is best.
Ammoniacal liquor and sodium borohydride is added, the pattern realizing cauliflower form brookite type titanium dioxide that can be controlled in presoma solvent of the present invention.
Preferably, precursor solution is deionized water and titanous chloride, and the concentration of titanous chloride is 0.08 ~ 8mol/L (preferred 0.8mol/L), concentration is higher than this scope or the pattern that all can not realize this cauliflower form brookite type titanium dioxide lower than this scope; Presoma solvent adds ammoniacal liquor and regulates pH to be 7 ~ 13 (preferably 11), and pH is higher than this scope or the pattern that can not realize this cauliflower form brookite type titanium dioxide lower than this scope.Contrast experiment sees comparative example 1; Presoma solvent adds sodium borohydride solution, and concentration is 1 ~ 10mol/L (preferred 2.5mol/L), and concentration is higher than this scope or the pattern that all can not realize this cauliflower form brookite type titanium dioxide lower than this scope.Simultaneous test is shown in comparative example 2; And sodium borohydride solution add 0.5 times that volume is precursor solution.
The titanic oxide material prepared is brookite type titanium dioxide; There is cauliflower form microballoon pattern; The pattern of this " cauliflower form " also belongs to the one of petal-shaped pattern.
Cauliflower form brookite type titanium dioxide particle diameter size of the present invention is 2 ~ 8 microns.
Hydrothermal method of the present invention is in tetrafluoroethylene reactor, take water as solvent, the chemical reaction carried out under the temperature condition of 250 DEG C.Reference: MingleiZhao.Afacilestrategytofabricatelarge-scaleuniform brookiteTiO2nanospindleswithhighthermalstabilityandsuper iorelectricalproperties.2013,49,7046-7048.
Described tetrafluoroethylene reactor is that hydrothermal synthesis reaction still makes again (high-pressure digestion tank, Pressure solution bullet) to be reactor for synthetic chemical under certain temperature, certain pressure condition provides.Advantage is: 1, erosion resistance is good, and unharmful substance overflows, decreasing pollution, use safety.2, after intensification, boosting, the dissolving of quick nondestructive ground the sample of dissolving and the sample containing volatile element can be difficult under normal conditions.3, appearance looks elegant, rational in infrastructure, simple to operate, shorten analysis time, data are reliable.
Preferably, in described step (A), the temperature of hydro-thermal reaction is 250 DEG C, and the hydro-thermal reaction time is 18 hours.
Preferred, described step (A) is specially and adds deionized water and titanous chloride in a kettle., makes the concentration of titanous chloride be 0.8mol/L.Then, then add ammoniacal liquor regulate pH to 11.Finally, add 2.5mol/L sodium borohydride solution, after stirring, mixed solution is placed in reactor, put into 250 DEG C of baking ovens, react 18 hours.
Preferably, adopt deionized water to titanium dioxide precipitation washing 3 ~ 6 times in described step (B), then use absolute ethanol washing 1 time, remove unreacted raw material, by product and other impurity.In described step (C), titanium dioxide precipitation is placed in 50-70 DEG C of (preferably 60 DEG C) vacuum drying oven dry, obtains cauliflower form brookite type titanium dioxide material.
For realizing above-mentioned second object, the technical scheme that the present invention takes is: a kind of cauliflower form brookite type titanium dioxide material, and described cauliflower form brookite type titanium dioxide material is prepared by above-mentioned method.Described titanic oxide material is brookite type titanium dioxide; There is cauliflower form microballoon pattern; Cauliflower form brookite type titanium dioxide particle diameter size is 2 ~ 8 microns.
The invention has the advantages that:
The present invention utilizes hydrothermal method, under mild conditions, can prepare cauliflower form brookite type titanium dioxide material fast, in a large number.Compared with prior art, the present invention has abundant raw material source, with low cost, technique is simple, reaction time is short, and prior art needs 2-3 days, as long as our 20 hours such as the following advantages, be suitable for the preparation preparing cauliflower form brookite type titanium dioxide material on a large scale, this brookite type titanium dioxide has important purposes in environmental science and new energy field.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern that embodiment 1 obtains product;
Fig. 2 is the scanning electron microscope diagram that embodiment 1 obtains product;
Fig. 3 is the scanning electron microscope diagram that embodiment 2 obtains product;
Fig. 4 is the scanning electron microscope diagram that embodiment 3 obtains product;
Fig. 5 is the scanning electron microscope diagram that embodiment 4 obtains product;
Fig. 6 is the scanning electron microscope diagram that embodiment 5 obtains product;
Fig. 7 is the scanning electron microscope diagram that embodiment 6 obtains product;
Fig. 8 is the scanning electron microscope diagram that comparative example 1 obtains product;
Fig. 9 is the scanning electron microscope diagram that comparative example 2 obtains product;
Figure 10 is the degradation effect figure of cauliflower form brookite type titanium dioxide of the present invention to tropeolin-D.
Embodiment
Below in conjunction with embodiment, embodiment provided by the invention is elaborated.
Embodiment 1
In the polytetrafluoroethyllining lining of reactor, add deionized water and titanous chloride, obtaining concentration is 0.8mol/L Titanium Trichloride Solution 20ml.Then, then add ammoniacal liquor regulate pH to 11.Finally, add the 2.5mol/L sodium borohydride solution of 10ml, after stirring, mixed solution is placed in high-temperature high-pressure reaction kettle, put into 250 DEG C of baking ovens, react 18 hours.
Question response still cool to room temperature, draws supernatant liquid and discards.By lower sediment deionized water wash 6 times, then use absolute ethanol washing 1 time.Throw out is put into 60 DEG C of baking oven vacuum-dryings 12 hours after having washed, obtain cauliflower form brookite type titanium dioxide material.
As shown in Figure 2, as can be seen from the figure, products obtained therefrom is by the titanium dioxide microballoon sphere of cauliflower form pattern to the scanning electron microscope (SEM) photograph of embodiment 1 products obtained therefrom.The X-ray diffraction spectrogram of embodiment 1 products obtained therefrom as shown in Figure 1, as can be seen from the figure, the diffraction peak of products obtained therefrom and the standard spectrogram (JCPDS:65-2448) of brookite titanium dioxide completely the same.
Embodiment 2
In the polytetrafluoroethyllining lining of reactor, add deionized water and titanous chloride, obtaining concentration is 0.8mol/L Titanium Trichloride Solution 20ml.Then, then add ammoniacal liquor regulate pH to 11.Finally, add the 2.5mol/L sodium borohydride solution of 10ml, after stirring, mixed solution is placed in high-temperature high-pressure reaction kettle, put into 250 DEG C of baking ovens, react 12 hours.
Question response still cool to room temperature, draws supernatant liquid and discards.By lower sediment deionized water wash 6 times, then use absolute ethanol washing 1 time.Throw out is put into 60 DEG C of baking oven vacuum-dryings 12 hours after having washed, obtain cauliflower form brookite type titanium dioxide material, Fig. 3 is the scanning electron microscopic picture of this sample.
Embodiment 3
In the polytetrafluoroethyllining lining of reactor, add deionized water and titanous chloride, obtaining concentration is 0.8mol/L Titanium Trichloride Solution 20ml.Then, then add ammoniacal liquor regulate pH to 11.Finally, add the 2.5mol/L sodium borohydride solution of 10ml, after stirring, mixed solution is placed in high-temperature high-pressure reaction kettle, put into 250 DEG C of baking ovens, react 24 hours.
Question response still cool to room temperature, draws supernatant liquid and discards.By lower sediment deionized water wash 6 times, then use absolute ethanol washing 1 time.Throw out is put into 60 DEG C of baking oven vacuum-dryings 12 hours after having washed, obtain cauliflower form brookite type titanium dioxide material, Fig. 4 is the scanning electron microscopic picture of this sample.
Embodiment 4
In the polytetrafluoroethyllining lining of reactor, add deionized water and titanous chloride, obtaining concentration is 0.8mol/L Titanium Trichloride Solution 20ml.Then, then add ammoniacal liquor regulate pH to 11.Finally, add the 2.5mol/L sodium borohydride solution of 10ml, after stirring, mixed solution is placed in high-temperature high-pressure reaction kettle, put into 250 DEG C of baking ovens, react 36 hours.
Question response still cool to room temperature, draws supernatant liquid and discards.By lower sediment deionized water wash 6 times, then use absolute ethanol washing 1 time.Throw out is put into 60 DEG C of baking oven vacuum-dryings 12 hours after having washed, obtain cauliflower form brookite type titanium dioxide material, Fig. 5 is the scanning electron microscopic picture of this sample.
Embodiment 5
In the polytetrafluoroethyllining lining of reactor, add deionized water and titanous chloride, obtaining concentration is 0.8mol/L Titanium Trichloride Solution 20ml.Then, then add ammoniacal liquor regulate pH to 11.Finally, add the 2.5mol/L sodium borohydride solution of 10ml, after stirring, mixed solution is placed in high-temperature high-pressure reaction kettle, put into 220 DEG C of baking ovens, react 18 hours.
Question response still cool to room temperature, draws supernatant liquid and discards.By lower sediment deionized water wash 3 times, then use absolute ethanol washing 1 time.Throw out is put into 60 DEG C of baking oven vacuum-dryings 12 hours after having washed, obtain cauliflower form brookite type titanium dioxide material, Fig. 6 is the scanning electron microscopic picture of this sample.
Embodiment 6
In the polytetrafluoroethyllining lining of reactor, add deionized water and titanous chloride, obtaining concentration is 0.8mol/L Titanium Trichloride Solution 20ml.Then, then add ammoniacal liquor regulate pH to 11.Finally, add the 2.5mol/L sodium borohydride solution of 10ml, after stirring, mixed solution is placed in high-temperature high-pressure reaction kettle, put into 280 DEG C of baking ovens, react 18 hours.
Question response still cool to room temperature, draws supernatant liquid and discards.By lower sediment deionized water wash 5 times, then use absolute ethanol washing 1 time.Throw out is put into 60 DEG C of baking oven vacuum-dryings 12 hours after having washed, obtain cauliflower form brookite type titanium dioxide material, Fig. 7 is the scanning electron microscopic picture of this sample.
Comparative example 1
In the polytetrafluoroethyllining lining of reactor, add deionized water and titanous chloride, obtaining concentration is 0.8mol/L Titanium Trichloride Solution 20ml.Then, then add ammoniacal liquor regulate pH to 3.Finally, add the 2.5mol/L sodium borohydride solution of 10ml, after stirring, mixed solution is placed in high-temperature high-pressure reaction kettle, put into 250 DEG C of baking ovens, react 18 hours.
Question response still cool to room temperature, draws supernatant liquid and discards.By lower sediment deionized water wash 3 times, then use absolute ethanol washing 1 time.Throw out is put into 60 DEG C of baking oven vacuum-dryings 12 hours after having washed, can not obtain cauliflower form brookite type titanium dioxide material, Fig. 8 is the scanning electron microscopic picture of this sample.
Comparative example 2
In the polytetrafluoroethyllining lining of reactor, add deionized water and titanous chloride, obtaining concentration is 0.8mol/L Titanium Trichloride Solution 20ml.Then, then add ammoniacal liquor regulate pH to 11.Finally, add the 1mol/L sodium borohydride solution of 10ml, after stirring, mixed solution is placed in high-temperature high-pressure reaction kettle, put into 250 DEG C of baking ovens, react 18 hours.
Question response still cool to room temperature, draws supernatant liquid and discards.By lower sediment deionized water wash 3 times, then use absolute ethanol washing 1 time.Throw out is put into 60 DEG C of baking oven vacuum-dryings 36 hours after having washed, can not obtain cauliflower form brookite type titanium dioxide material, Fig. 9 is the scanning electron microscopic picture of this sample.
Application examples 1
For the cauliflower form brookite type titanium dioxide of embodiment 1, the catalytic effect of checking inventive samples, its step is as follows:
1. get the cauliflower form brookite type titanium dioxide (embodiment 1 sample) of 50mg, add in the methyl orange solution of 25mg10mg/L;
2. methyl orange solution is stirred 30min at dark place, solution is made to be in adsorption equilibrium state, then irradiate under ultraviolet lamp (12W), at suitable reaction times point (30min, 60min, 90min, 120min) take out 2ml reaction solution respectively and carry out absorption test, measure the absorbancy of tropeolin-D in now solution, calculate concentration according to langbobier law, calculate sampling concentration concentration proportion orange with initial;
3. be X-coordinate with time, sampling concentration and starting point concentration ratio are ordinate zou, curve plotting, as shown in Figure 10; As can be seen from the figure: cauliflower form brookite type titanium dioxide of the present invention has certain photocatalytic degradation effect, and within the time of 120min, degradation efficiency can reach 5.62%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the inventive method; can also make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.
Claims (9)
1. the preparation method of a cauliflower form brookite type titanium dioxide, it is characterized in that, comprise the following steps: (A) adopts hydrothermal method to prepare titanic oxide material: under agitation condition, titanium source precursor solution is added ammoniacal liquor and sodium borohydride solution, at 220 ~ 280 DEG C, hydro-thermal reaction 12 ~ 36 hours, obtains titanium dioxide precipitation; (B) wash; (C) vacuum-drying, obtains cauliflower form brookite type titanium dioxide material.
2. preparation method according to claim 1, is characterized in that, described titanium source presoma is titanous chloride.
3. preparation method according to claim 2, it is characterized in that, in described step (A), precursor solution is deionized water and titanous chloride, and the concentration of titanous chloride is 0.08 ~ 8mol/L, precursor solution adds ammoniacal liquor and regulates pH to be 7 ~ 13, the sodium borohydride solution concentration added is 1 ~ 10mol/L, and sodium borohydride solution add 0.5 times that volume is precursor solution.
4. preparation method according to claim 1, is characterized in that, in described step (A), the temperature of hydro-thermal reaction is 250 DEG C, and the hydro-thermal reaction time is 18 hours.
5. preparation method according to claim 1, is characterized in that, adopts deionized water to titanium dioxide precipitation washing 3 ~ 6 times, then uses absolute ethanol washing 1 time, remove unreacted raw material, by product and other impurity in described step (B).
6. preparation method according to claim 1, is characterized in that, in described step (C), titanium dioxide precipitation is placed in 50-70 DEG C of vacuum drying oven dry, obtains cauliflower form brookite type titanium dioxide material.
7. preparation method according to claim 1, is characterized in that, described titanic oxide material is brookite type titanium dioxide; There is cauliflower form microballoon pattern; Described cauliflower form brookite type titanium dioxide particle diameter size is 2 ~ 8 microns.
8. a cauliflower form brookite type titanium dioxide material, is characterized in that, described cauliflower form brookite type titanium dioxide material is prepared by the arbitrary described preparation method of claim 1-7.
9. cauliflower form brookite type titanium dioxide material according to claim 8, is characterized in that, described titanic oxide material is brookite type titanium dioxide; There is cauliflower form microballoon pattern; Described cauliflower form brookite type titanium dioxide particle diameter size is 2 ~ 8 microns.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510874530.3A CN105417578B (en) | 2015-12-02 | 2015-12-02 | A kind of preparation method of cauliflower-shaped brookite type titanium dioxide |
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|---|---|---|---|
| CN201510874530.3A CN105417578B (en) | 2015-12-02 | 2015-12-02 | A kind of preparation method of cauliflower-shaped brookite type titanium dioxide |
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| Publication Number | Publication Date |
|---|---|
| CN105417578A true CN105417578A (en) | 2016-03-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076302A (en) * | 2016-06-06 | 2016-11-09 | 中国科学院新疆理化技术研究所 | A kind of preparation method of nanometer black titanium dioxide optical catalyst |
| CN112744858A (en) * | 2021-01-08 | 2021-05-04 | 孙淑珍 | Solvothermal preparation method of titanium suboxide powder |
| CN113697853A (en) * | 2021-08-28 | 2021-11-26 | 上海大学 | Titanium suboxide and preparation method thereof |
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| CN103771505A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide self-assembled particles |
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| CN103771505A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide self-assembled particles |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076302A (en) * | 2016-06-06 | 2016-11-09 | 中国科学院新疆理化技术研究所 | A kind of preparation method of nanometer black titanium dioxide optical catalyst |
| CN112744858A (en) * | 2021-01-08 | 2021-05-04 | 孙淑珍 | Solvothermal preparation method of titanium suboxide powder |
| CN113697853A (en) * | 2021-08-28 | 2021-11-26 | 上海大学 | Titanium suboxide and preparation method thereof |
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