CN102689917B - Method for preparing barium sulfate porous microspheres and titanium dioxide nano-particles by using titanium sulfate - Google Patents
Method for preparing barium sulfate porous microspheres and titanium dioxide nano-particles by using titanium sulfate Download PDFInfo
- Publication number
- CN102689917B CN102689917B CN201210194228.XA CN201210194228A CN102689917B CN 102689917 B CN102689917 B CN 102689917B CN 201210194228 A CN201210194228 A CN 201210194228A CN 102689917 B CN102689917 B CN 102689917B
- Authority
- CN
- China
- Prior art keywords
- titanium
- sulfate
- titanium dioxide
- barium sulfate
- polyvinylpyrrolidone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 60
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 28
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 title claims abstract description 24
- 229910000348 titanium sulfate Inorganic materials 0.000 title claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 23
- 239000004005 microsphere Substances 0.000 title claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229940045511 barium chloride Drugs 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 titanic acid ester Chemical class 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Images
Abstract
The invention discloses a method for preparing barium sulfate porous microspheres and titanium dioxide nano-particles by using titanium sulfate as a raw material, which comprises the following steps that after being evenly mixed, a titanium sulphate solution containing polyvinylpyrrolidone and hydrogen peroxide and a barium chloride solution containing polyvinylpyrrolidone react in a reaction kettle at a certain temperature, and then are naturally cooled to room temperature, and then the resultant product is centrifugally separated to obtain a precipitate and a supernatant; the precipitate is washed and dried to obtain barium sulfate porous microspheres; and after being added with an appropriate amount of urea, the supernatant is placed in an autoclave to be reacted at a certain temperature and then is naturally cooled to room temperature, and the resultant product is centrifugally separated, washed and dried to obtain mono-dispersed titanium dioxide nanoparticles. According to the method for preparing the barium sulfate porous microspheres and the titanium dioxide nano-particles by using the titanium sulfate as the raw material, the raw material is cheap, and the method is simple. The product barium sulfate microspheres have a porous structure or a hollow structure, the morphology is easy to control, and the specific surface area is large. The product titanium dioxide nano-particle has a uniform size and good dispersibility.
Description
Technical field
The invention belongs to new chemical materials field, the preparation method who relates to a kind of barium sulfate microballoon and monodisperse titanium dioxide nanometer particle, specifically, relate to a kind ofly take titanium sulfate and prepare the liquid phase preparation process of barium sulfate porous microsphere and monodisperse titanium dioxide nanometer particle as raw material.
Background technology
Titanium dioxide has broad application prospects in field of environment protection as a kind of photocatalyst, is the semiconductor light-catalyst of studying at present at most.In recent years the preparation research of nano titanium oxide is also quite goed deep into extensive.For example, Chinese patent CN 101597083A discloses a kind of preparation method of monodisperse nano-titanium dioxide, and the method be take titanic acid ester as presoma, under tensio-active agent exists, carries out solvent thermal reaction anatase-type nanometer titanium dioxide in ethanol.Chinese patent CN 101073769A has announced a kind of steam hydrolysis legal system for the method for nano titanium oxide, and the method utilizes the hydrolysis reaction of titanium tetrachloride in ethanolic soln to prepare titanium dioxide nano-particle, obtains crystal titanium dioxide after roasting.It should be noted that the inorganic titanium tetrachloride that mostly uses organo-metallic titanium precursor thing or difficult operation in existing preparation method, but also will be with an organic solvent, preparation cost is high.
Barium sulfate is a kind of important inorganic materials, is widely used in the fields such as various coating, paint, ink, the synthetic chemical industry of medicine, rubber, plastics, papermaking, pottery, weaving, makeup.But because its proportion is high, and its application performance is restricted.
At present, the main development trend of barium sulfate powder is the granular of its particle and the variation of structural form, to meet the special requirement of different industries.The method of preparing barium sulfate fine particle mainly contains microemulsion method, complexometry, microreactor method, gravity Method etc.For example, Chinese patent CN1398789A has announced a kind of preparation method of nano barium sulfate, and take bariumchloride and EDTA solution is raw material, and the two mixing is made to Ba
2+ion and EDTA complexing add Na under certain pH
2sO
4solution reacts, and obtains nano barium sulfate product.Chinese patent CN102167386 A discloses a kind of micropore dispersion legal system of liquid phase cross-flow shearing of utilizing for the method for barium sulfate nanoparticles.Chinese patent CN101423239 A has announced a kind of method that rotating liquid-film reactor that utilizes high speed rotating is prepared nano barium sulfate.But prepared barium sulphate nano powder also exist because reunion makes specific surface area diminish, complex process, gained pattern be difficult to the shortcomings such as control, is difficult to meet the requirement of Vehicles Collected from Market to the increasing property of barium sulfate powder (as lightweight, inhale make an uproar etc.).
Summary of the invention
The present invention is directed to the complex technical process of gained barium sulfate sample in prior art, reaction conditions is harsher, the problems such as powder microstructure is single, and in existing Preparation Technology of Nanometer Titanium Dioxide, use the problems such as metal organic titanate and organic solvent, proposed that a kind of technique is relatively simple, reaction conditions is gentleer, utilize inorganic titanium sulfate to prepare the method for porous barium sulfate microballoon and titanium dioxide nano-particle, take full advantage of the titanium resource of high value in inorganic titanium sulfate.The present invention is achieved by the following technical solutions:
A method of being prepared barium sulfate porous microsphere and titanium dioxide nano-particle by titanium sulfate, described method comprises the steps:
(1) titanium sulfate, polyvinylpyrrolidone (PVP) are dissolved in the water, then add a certain amount of superoxol, obtain certain density titanium sulfate solution;
(2) a certain amount of bariumchloride and polyvinylpyrrolidone are dissolved in the water, obtain certain density barium chloride solution;
(3) above-mentioned two kinds of solution are mixed according to a certain volume, transfer in reactor, react for some time at a certain temperature, then naturally cool to room temperature;
(4) by above-mentioned reaction solution centrifugation, obtain white precipitate and supernatant liquor;
(5) by after the throw out water and ethanol repeated washing that obtain in step (4), put into 60-80 ℃ of loft drier dry, obtain barium sulfate target product;
(6) supernatant liquor obtaining in step (4) is placed in to autoclave, and adds appropriate urea to dissolve, after reaction, naturally cool to room temperature at a certain temperature;
(7) by the reaction solution centrifugation in step (6), will precipitate after water and ethanol repeated washing, put into 60-80 ℃ of loft drier dry, obtain titanium dioxide target product.
Wherein, in step (1), the mass ratio of polyvinylpyrrolidone and titanium sulfate is 1:1-1:10, and the mol ratio of titanium sulfate and superoxol is 1:0-1:10;
Wherein, in step (2), the mass ratio of polyvinylpyrrolidone and bariumchloride is 1:1-1:10;
Wherein, in step (3), the mol ratio of titanium sulfate and bariumchloride is 1:1, and temperature of reaction is 150-200 ℃, and the reaction times is 6-24 h;
Wherein, in step (4), described centrifugal rotational speed is 3000-4000 r/min, and centrifugation time is 5-10min;
Wherein, in step (6), the concentration of urea is 10-20 mmol/L, and temperature of reaction is 150-200 ℃, and the reaction times is 10-24 h;
Wherein, in step (7), described centrifugal rotational speed is 6000-8000 r/min, and centrifugation time is 5-10min;
The invention has the advantages that: precursor used is cheap inorganic salt titanium sulfate, in the aqueous solution, reacts, and preparation cost is low; The nano-TiO that the method is prepared
2particle shape homogeneous, good dispersity.The barium sulfate microballoon of preparation is vesicular structure, good dispersity.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo (TEM) of the prepared barium sulfate sample of embodiment mono-.
Fig. 2 is the transmission electron microscope photo (TEM) of the prepared titanium dioxide sample of embodiment mono-.
Embodiment
Below by embodiment, the present invention is described in further detail:
embodiment mono-:
(1) titanium sulfate is dissolved in the water, then after adding 0.1 g polyvinylpyrrolidone to dissolve, adds the superoxol of 0.14 ml, obtain the titanium sulfate solution of 2.5 mmol/L;
(2) bariumchloride is dissolved in the water, then adds 0.1 g polyvinylpyrrolidone to dissolve, obtain the barium chloride solution of 2.5 mmol/L;
(3) after above-mentioned two kinds of solution equal-volumes are mixed, transfer in reactor, at 180 ℃, react 24 h, then naturally cool to room temperature, obtain the mixed solution that contains barium sulfate;
(4) by the centrifugation under 3000 r/min of above-mentioned reaction solution, obtain white precipitate and supernatant liquor;
(5) by after the throw out water and ethanol repeated washing that obtain in step (4), put into 60 ℃ of loft drier dry, obtain barium sulfate microballoon target product;
(6) supernatant liquor obtaining in step (4) is placed in to autoclave, and adds appropriate urea to dissolve, reaching concentration is 20 mmol/L, after 180 ℃ of reaction 20 h, naturally cools to room temperature.
(7) by the centrifugal 5min of 6000 r/min of the reaction solution in step (6), isolate precipitation, will precipitate after water and ethanol repeated washing, put into 80 ℃ of loft drier dry, obtain titanium dioxide target product.
Fig. 1 is the transmission electron microscope photo (TEM) that utilizes barium sulfate porous microsphere prepared by the method for the invention.As can be seen from Fig., barium sulfate microspherulite diameter is evenly distributed, and is obviously hollow, vesicular structure, and size is 600 nanometer left and right.
Fig. 2 is the transmission electron microscope photo (TEM) that utilizes titanium dioxide sample prepared by the method for the invention, from photo, can find out, prepared titanium dioxide granule is better dispersed, and particle diameter is mostly tens nanometers.
embodiment bis-:
(1) titanium sulfate is dissolved in the water, then after adding 0.1 g polyvinylpyrrolidone to dissolve, adds the superoxol of 0.07 ml, obtain the titanium sulfate solution of 2.5 mmol/L;
(2) bariumchloride is dissolved in the water, then adds 0.1 g polyvinylpyrrolidone to dissolve, obtain the barium chloride solution of 2.5 mmol/L;
(3) after above-mentioned two kinds of solution equal-volumes are mixed, transfer in reactor, at 180 ℃, react 18 h, then naturally cool to room temperature, obtain the mixed solution that contains barium sulfate;
(4) by the centrifugation under 3000 r/min of above-mentioned reaction solution, obtain white precipitate and supernatant liquor;
(5) by after the throw out water and ethanol repeated washing that obtain in step (4), put into 60 ℃ of loft drier dry, obtain barium sulfate microballoon target product;
(6) supernatant liquor obtaining in step (4) is placed in to autoclave, and to add appropriate urea concentration of ordinary dissolution be 10 mmol/L, after 150 ℃ of reaction 20 h, naturally cool to room temperature.
(7) by the centrifugal 10min of 8000 r/min of the reaction solution in step (6), isolate precipitation, will precipitate after water and ethanol repeated washing, put into 80 ℃ of loft drier dry, obtain titanium dioxide target product.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any change of doing in the situation that not deviating from principle of the present invention and technological process, substitute, simplification etc.; be equivalent displacement, within all protection scope of the present invention should being included in.
Claims (4)
1. by titanium sulfate, prepared a method for barium sulfate porous microsphere and monodisperse titanium dioxide nanometer particle, it is characterized in that, described method comprises the steps:
(1) titanium sulfate, polyvinylpyrrolidone (PVP) are dissolved in the water, then add superoxol, obtain titanium sulfate solution;
(2) bariumchloride and polyvinylpyrrolidone are dissolved in the water, obtain barium chloride solution;
(3) by above-mentioned titanium sulfate solution and barium chloride solution in molar ratio for the ratio of 1:1 mixes, transfer in reactor, in temperature of reaction, be to react 6-24h at 150-200 ℃;
(4) by above-mentioned reaction solution centrifugation, obtain white precipitate and supernatant liquor;
(5) by after the white precipitate water and ethanol repeated washing that obtain in step (4), put into 60-80 ℃ of loft drier dry, obtain barium sulfate porous microsphere;
(6) supernatant liquor obtaining in step (4) being placed in to autoclave, and adding urea to dissolve, is to react after 10-24h at 150-200 ℃ in temperature of reaction, naturally cools to room temperature;
(7) by the reaction solution centrifugation in step (6), will precipitate after water and ethanol repeated washing, put into 60-80 ℃ of loft drier dry, obtain monodisperse titanium dioxide nanometer particle;
In step (1), the mass ratio of polyvinylpyrrolidone and titanium sulfate is 1:1-1:10, and the mol ratio of titanium sulfate and superoxol is 1:0-1:10.
In step (2), the mass ratio of polyvinylpyrrolidone and bariumchloride is 1:1-1:10.
2. method according to claim 1, is characterized in that, in step (4), described centrifugal rotational speed is 3000-4000r/min, and centrifugation time is 5-10min.
3. method according to claim 1, is characterized in that, in step (6), the concentration of urea is 10-20mmol/L.
4. method according to claim 1, is characterized in that, in step (7), described centrifugal rotational speed is 6000-8000r/min, and centrifugation time is 5-10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210194228.XA CN102689917B (en) | 2012-06-13 | 2012-06-13 | Method for preparing barium sulfate porous microspheres and titanium dioxide nano-particles by using titanium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210194228.XA CN102689917B (en) | 2012-06-13 | 2012-06-13 | Method for preparing barium sulfate porous microspheres and titanium dioxide nano-particles by using titanium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102689917A CN102689917A (en) | 2012-09-26 |
| CN102689917B true CN102689917B (en) | 2014-05-07 |
Family
ID=46855677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210194228.XA Expired - Fee Related CN102689917B (en) | 2012-06-13 | 2012-06-13 | Method for preparing barium sulfate porous microspheres and titanium dioxide nano-particles by using titanium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102689917B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107074581A (en) * | 2014-09-30 | 2017-08-18 | 住友大阪水泥股份有限公司 | Manufacture method, Titanium particles, the dispersion soln of Titanium particles, titania slurry, oxidation titanium film and the DSSC of Titanium particles |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739013A (en) * | 2014-01-07 | 2014-04-23 | 天津大学 | Porous spherical titanium dioxide with controllable diameter and preparation and application thereof |
| CN108675346B (en) * | 2018-06-05 | 2021-02-02 | 青岛科技大学 | TiO 22(B) Method for preparing microspheres |
| CN108854398A (en) * | 2018-07-24 | 2018-11-23 | 苏州水木康桥环境工程技术有限公司 | A kind of photolytic activity carbon purifying device |
| CN113462198A (en) * | 2021-08-12 | 2021-10-01 | 佛山集美精化科技有限公司 | Method for preparing composite titanium dioxide by barium sulfate coprecipitation method |
| CN115924954A (en) * | 2022-12-28 | 2023-04-07 | 佛山安亿纳米材料有限公司 | Preparation method and application of mesoporous barium sulfate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398789A (en) * | 2002-08-13 | 2003-02-26 | 华北工学院 | Prepn of nano barium sulfate |
| CN1969017A (en) * | 2004-05-04 | 2007-05-23 | 纳米技术应用中心（Can）股份有限公司 | Process for preparing dispersible sulfate, preferably barium sulfate nanoparticles |
-
2012
- 2012-06-13 CN CN201210194228.XA patent/CN102689917B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398789A (en) * | 2002-08-13 | 2003-02-26 | 华北工学院 | Prepn of nano barium sulfate |
| CN1969017A (en) * | 2004-05-04 | 2007-05-23 | 纳米技术应用中心（Can）股份有限公司 | Process for preparing dispersible sulfate, preferably barium sulfate nanoparticles |
Non-Patent Citations (4)
| Title |
|---|
| "水热沉淀法制备TiO2纳米粉体的研究";黄晖等;《硅酸盐通报》;20001231(第4期);第8-12页 * |
| "纳米氧化物的制备与性能研究";杨茂丽;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20110415;B020-165 ，正文第53-57页 * |
| 杨茂丽."纳米氧化物的制备与性能研究".《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2011,B020-165 ，正文第53-57页. |
| 黄晖等."水热沉淀法制备TiO2纳米粉体的研究".《硅酸盐通报》.2000,(第4期),第8-12页. |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107074581A (en) * | 2014-09-30 | 2017-08-18 | 住友大阪水泥股份有限公司 | Manufacture method, Titanium particles, the dispersion soln of Titanium particles, titania slurry, oxidation titanium film and the DSSC of Titanium particles |
| EP3202716A4 (en) * | 2014-09-30 | 2018-05-02 | Sumitomo Osaka Cement Co., Ltd. | Method for producing titanium oxide particles, titanium oxide particles, dispersion solution of titanium oxide particles, titanium oxide paste, titanium oxide film and dye-sensitized solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102689917A (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102689917B (en) | Method for preparing barium sulfate porous microspheres and titanium dioxide nano-particles by using titanium sulfate | |
| CN103708551B (en) | The preparation method of a kind of ethylene glycol-water mixed solvent thermal synthesis bismuth oxycarbonate flower-like microsphere | |
| CN101302032B (en) | Preparation of cupric oxide nano-material | |
| CN102649589B (en) | Fibroin-controlled alpha type ferric oxide nano material and preparation method thereof | |
| CN104787769B (en) | A kind of method that silicon dioxide hollow microsphere is prepared with template | |
| CN101475211A (en) | Preparation of nano composite multi-layer oxide hollow microsphere | |
| CN101333002B (en) | Titanium dioxide nanometer powder with special appearance and method for preparing same | |
| CN102633307A (en) | Method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles | |
| CN102786097A (en) | Hydrothermal preparation method for carbon cladded nanometer ferriferrous oxide particles | |
| JP2015009238A (en) | Metal oxide composite including hollow core and porous shell layer and method for manufacturing the same | |
| CN101745352A (en) | Superhydrophobic surface material and special nano-particles thereof with core-shell structures | |
| CN1198884C (en) | Preparation method of spherical composite nano silver/silicon dioxide functional material | |
| CN103880073B (en) | Method for preparing nano titanium dioxide by applying precipitation process and adopting microreactor | |
| CN101428220A (en) | Magnetic titanium dioxide hollow ball and preparation method thereof | |
| CN104310468B (en) | One prepares the method for monodisperse titanium dioxide (B) nanoparticle | |
| CN105271405A (en) | Material based on bismuth oxycarbonate or bismuth oxide nano tube and preparation method thereof | |
| CN103691433A (en) | Ag-doped TiO2 material, and preparation method and application thereof | |
| CN105502463A (en) | Preparation method of hollow calcium carbonate microspheres of micro-scale and nano-scale pore structures | |
| CN108654675A (en) | A kind of g-C3N4/TiO2(B) preparation method of complex microsphere | |
| CN104439276B (en) | A kind of quick method and product preparing hollow porous silica/argentum nano composite material | |
| CN104746178B (en) | A kind of preparation method of the silicate double-layer hollow nanofiber with multilevel hierarchy | |
| CN104891567A (en) | Preparing method of tubular TiO2/reduced graphene oxide composite | |
| CN101143974A (en) | Method for preparing composite nano particle of silicon dioxide coated with zinc oxide | |
| CN101891974A (en) | Method for preparing TiO2/SiO2 composite powder | |
| CN105329932A (en) | Method for large-scale preparation of carbon-doped mixed transition metal oxide porous microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191121 Address after: No. 56, South Tianyang Road, Tianning Town, Jiashan County, Jiaxing City, Zhejiang Province Patentee after: JIASHAN HUAYANG WOOD INDUSTRY FLOCKING CO., LTD. Address before: 266061 Shandong Province, Qingdao city Laoshan District Songling Road No. 99, Qingdao University of Science & Technology Patentee before: Qingdao University of Science & Technology |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140507 Termination date: 20210613 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |