CN100434178C - Process for preparing titanium dioxide photo catalyst - Google Patents
Process for preparing titanium dioxide photo catalyst Download PDFInfo
- Publication number
- CN100434178C CN100434178C CNB2006100247724A CN200610024772A CN100434178C CN 100434178 C CN100434178 C CN 100434178C CN B2006100247724 A CNB2006100247724 A CN B2006100247724A CN 200610024772 A CN200610024772 A CN 200610024772A CN 100434178 C CN100434178 C CN 100434178C
- Authority
- CN
- China
- Prior art keywords
- tio
- collosol
- temperature
- titanium
- catalyst
- 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
Images
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a preparation method for a TiO2 photocatalyst. The present invention comprises the following steps: glycerol is slowly dropped into absolute alcohol at normal temperature and stirred to obtain a solution A; titanium precursors are slowly dropped in the A solution and thoroughly stirred to obtain uniform and transparent TiO2 collosol; ether is added into the obtained A collosol and continuously stirred to obtain collosol B; the collosol B is transferred into a hydrothermal kettle and stands for 1d to 7d at the temperature of 363 to 403K; the collosol B is taken out and naturally cooled to room temperature; the collosol B is washed by an ethanol wash solution to no color, and TiO2 microparticles are obtained through vacuum filtration and drying; the pure TiO2 powder is placed in a muffle furnace and calcined to obtain the TiO2 photocatalyst. The method of the present invention has the advantages of low synthesis process requirement, low cost, etc., and the TiO2 particles manufactured by the method of the present invention have the advantages of low-density, high activity, high purity, etc.
Description
Technical field
The present invention relates to a kind of technology of preparing of photochemical catalyst, be specifically related to a kind of TiO
2The preparation method of photochemical catalyst.
Background technology
Photocatalysis is a research direction that constantly develops in catalytic field in recent years, compares with traditional heterogeneous catalysis process, utilizes sunshine, non-secondary pollution, cleaning, safety, efficient.Therefore have wide practical use in fields such as new energy development, cleaning procedure, environmental protection, become one of focus of catalysis worker research.In recent years, utilize that all contaminations has caused World Focusing in the semiconductor light-catalyst processing environment, the conductor photocatalysis degradation of organic substances is significant aspect environmental improvement.TiO
2Nontoxic with it, catalytic activity is high, chemical stability good, cheap and easy to get and can directly utilize advantages such as sunshine to be subject to people's attention, and become typical photochemical catalyst.Preparation TiO
2The conventional method of photochemical catalyst is to adopt earlier the So1-gel legal system to be equipped with body attitude before the catalyst, carries out convection drying and high-temperature roasting after the heat treatment and obtains superfine Ti O
2Particle.But the employing snead process can cause the sample inequality of being heated, and the existence of gas-liquid interface interfacial surface tension in addition is difficult to keep the even integrality of former gel rubber system network structure, and particle aggregation takes place when high-temperature roasting easily, makes TiO
2The powder densification, the density height, heat endurance is relatively poor, and crystal transfer takes place easily.Chang Yong titanium dioxide optical catalyst mostly is the catalyst of German Degussa P25 one class in the market, because condition harshness, difficulty that such catalyst gas phase is synthesized are big, and equipment requirement condition height, synthesis technique requires high, exists many deficiencies.
Summary of the invention
Technical problem to be solved by this invention provides a kind of heat treatment of adopting solvent-thermal method to be applied to preceding body attitude, makes directly ageing in water heating kettle of colloidal sol, can effectively overcome the defective that colloidal sol exists at direct drying method, obtains low, the active high pure TiO of density
2The preparation method of particle.
The technical problem that the present invention solves can realize by following technical scheme.
1, a kind of TiO
2The preparation method of photochemical catalyst may further comprise the steps:
(1) normal temperature slowly splashes into glycerine in the absolute ethyl alcohol, fully stirs, and obtains solution A; The A colloidal sol that predecessor slowly splashes in the A solution and fully stirring 0.5-2h obtains homogeneous transparent with titanium; Wherein the volume ratio of the predecessor of titanium, glycerine and absolute ethyl alcohol is 0.5-2: 10: 20;
(2) ether is joined in the resulting A colloidal sol, continue to stir 10min-20min, get sol B; The volumn concentration that adds ether accounts for the 14%-40% of cumulative volume;
(3) sol B is transferred in the water heating kettle, left standstill under the 363-403K temperature 1 day-7 days, take out and naturally cool to room temperature, the taking-up white depositions is colourless to the ethanol washing lotion with ethanol washing several times, puts into 100 ℃ oven drying behind the suction filtration, obtains TiO
2Particulate;
(4) with the TiO of gained
2Particulate places Muffle furnace, is warming up to the 623-973K roasting 180-600 minute with the programming rate of 2K/min.
The predecessor of described titanium is selected from a kind of in titanium tetrachloride, butyl titanate, tetraethyl titanate or the isopropyl titanate.
The predecessor of described titanium preferably uses titanium tetrachloride.
The preparation temperature of described A solution is 278-313K.
Digestion time the best of described step (3) is 2 days, and the ageing temperature is 382-384K.
Used titanium tetrachloride, ether, phenol and glycerine all is chemical pure or analyzes purely in the above-mentioned experimental procedure, and all solution all dispose in deionized water.
Below by the light-catalyzed reaction between catalyst of the present invention and the phenol, Application of Catalyst effect of the present invention is described.
Determine actual density by weighing method and BET method and list in table 1 with relevant structural parameters:
The structural parameters of the photochemical catalyst of the different sintering temperatures of table 1
| Sample number into spectrum | Sintering temperature (℃) | Specific area (cc/g) | Density (kg/m 3) |
| 350#-1 | 350 | 45 | 80 |
| 400#-1 | 400 | 41 | 82 |
| 500#-1 | 500 | 32 | 84 |
| 550#-1 | 550 | 27 | 84 |
| 600#-1 | 600 | 21 | 85 |
| 700#-1 | 700 | 16 | 220 |
| P25 | ND | 54 | 140 |
TiO with above-mentioned numbering
2Catalyst sample is respectively applied for the reaction of phenol liquid phase photocatalytic degradation, reaction 2h, result such as accompanying drawing 1 under 3 uviol lamps (characteristic wavelength is each 8W of 254nm) irradiation.As seen along with the increase of sintering temperature, the active rising earlier afterwards reduced by accompanying drawing 1.Along with the rising of sintering temperature, TiO
2Crystal formation be transformed into rutile gradually by anatase, and crystalline phase is complete gradually.Anatase phase is best in the time of 550 ℃, and makes catalyst activity reach the quite active of best and traditional P25.Temperature raises again, and its active decline appears making in rutile.The catalyst XRD figure of its different sintering temperatures such as accompanying drawing 2.
From above-mentioned data as can be seen, adopt solvent-thermal method to be applied to the TiO of the heat treatment method acquisition of preceding body attitude
2Particle is compared with German Degussa P25 catalyst, and in the reaction of phenol liquid phase photocatalytic degradation, both have equal photocatalytic activity.
The heat treatment of body attitude before the present invention adopts solvent-thermal method to be applied to, make directly ageing in water heating kettle of colloidal sol, can effectively overcome the defective that colloidal sol exists at direct drying method, adopt the inventive method to have low, the low cost and other advantages of synthesis technique requirement, and the TiO that makes by the inventive method
2Particle has advantages such as low, the active height of density, high-purity.
Description of drawings
Accompanying drawing 1 is the present invention catalyst Pyrogentisinic Acid's when different sintering temperature degraded graph of a relation;
The XRD figure of the catalyst of accompanying drawing 2 the present invention when different sintering temperature.
The specific embodiment
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1
Under the normal temperature, the glycerine of 10mL is slowly splashed in the 20mL absolute ethyl alcohol, fully stir, obtain solution A; The titanium tetrachloride of getting different volumes (0.5mL, 1mL, 1.5mL, 2mL) respectively splashes in the A solution and vigorous stirring, waits to drip off the back and continues to stir the TiO that 30min obtains homogeneous transparent
2Colloidal sol; The 10ml ether is joined resulting TiO
2In the colloidal sol, continue to stir 10min, get sol B; Sol B is transferred in the 50mL water heating kettle, kept temperature 383K, place 2d, take out and naturally cool to room temperature; It is colourless to ethanol with ethanol washing 3 times to take out white depositions, and the baking oven of putting into 100 ℃ behind the suction filtration is dry; With the TiO that obtains
2Particulate rises to 823K roasting 240min with the heating rate of 2K/min, and the catalyst granules of gained is directly used in the reaction of phenol liquid phase photocatalytic degradation.
Determine actual density by weighing method and BET method and list in table 1 with relevant structural parameters:
The structural parameters of the photochemical catalyst of the different sintering temperatures of table 1
| Sample number into spectrum | Sintering temperature (℃) | Specific area (cc/g) | Density (kg/m 3) |
| 350#-1 | 350 | 45 | 80 |
| 400#-1 | 400 | 41 | 82 |
| 500#-1 | 500 | 32 | 84 |
| 550#-1 | 550 | 27 | 84 |
| 600#-1 | 600 | 21 | 85 |
| 700#-1 | 700 | 16 | 220 |
| P25 | ND | 54 | 140 |
Above-mentioned catalyst is applied to the reaction of liquid phase phenol photocatalytic degradation, temperature 303.0K time 2h; The initial concentration of phenol is 0.1 grams per liter, volume 50mL; Catalyst amount 0.05 gram; Three of light source 254nm, power averaging 8W).Result such as accompanying drawing 1 and accompanying drawing 2.
Table 2 catalyst is reused the relation of number of times and degradation rate
| Reaction times | Reaction time | Separate rate (550#-1) | Degradation rate (600#-1) |
| 1 | 2h | 99％ | 88％ |
| 2 | 2h | 98％ | 87％ |
| 3 | 2h | 98％ | 86％ |
| 4 | 2h | 97％ | 86％ |
| 5 | 2h | 96％ | 86％ |
| 6 | 2h | 96％ | 84％ |
| 7 | 2h | 96％ | 84％ |
| 8 | 2h | 95％ | 84％ |
As seen along with the increase of sintering temperature, the active rising earlier afterwards reduced by bow Fig. 1 and accompanying drawing 2.This chief reason is exactly the rising along with sintering temperature, TiO
2Crystal formation be transformed into rutile gradually by anatase, and crystalline phase is complete gradually.Table 2 data show: anatase phase is best in the time of 550 ℃, and makes catalyst activity reach the quite active of best and traditional P25.
Embodiment 2
Adopt method similarly to Example 1 to prepare pure TiO
2Photochemical catalyst, difference are that the ether consumption has only been taken 5mL, 30ml, TiO
2The part-structure parameter of photochemical catalyst is listed in table 3.
The structural parameters of the photochemical catalyst of the different ether amounts of table 3
| Sample number into spectrum | Ether amount (m1) | Sintering temperature (℃) | Specific area (cc/g) | Density (kg/m 3) |
| 550#-1 | 10 | 550 | 27 | 84 |
| 550#-2 | 5 | 550 | 26 | 87 |
| 550#-3 | 30 | 550 | 21 | 200 |
Above-mentioned catalyst is applied to the reaction of liquid phase phenol photocatalytic degradation, temperature 303.0K time 2h; The initial concentration of phenol is 0.1 grams per liter, volume 50mL; Catalyst amount 0.05 gram; Three of light source 254nm, power averaging 8W).Result such as table 4,5
The photochemical catalyst Pyrogentisinic Acid's of the different ether amounts of table 4 degraded
| Sample number into spectrum | Ether amount (ml) | Degradation rate (2h) |
| 550#-1 | 10 | 99％ |
| 550#-2 | 5 | 97％ |
| 550#-3 | 30 | 83％ |
Table 5 catalyst is reused the relation of number of times and degradation rate
| Reaction times | Reaction time | Degradation rate (550#-1) | Degradation rate (550#-2) | Degradation rate (550#-3) |
| 1 | 2h | 99％ | 97％ | 83％ |
| 2 | 2h | 98％ | 96％ | 83％ |
| 3 | 2h | 98％ | 96％ | 82％ |
| 4 | 2h | 97％ | 96％ | 82％ |
| 5 | 2h | 96％ | 96％ | 82％ |
| 6 | 2h | 96％ | 95％ | 81％ |
| 7 | 2h | 96％ | 95％ | 80％ |
| 8 | 2h | 95％ | 95％ | 80％ |
Visible by table 4 in the many influences very big again of ether amount to catalyst density.Amount is few not to have too much influence substantially, but still can see variation tendency, and density also can reduce very little, so that the 10ml ether is only is best, otherwise all is unfavorable for activity of such catalysts too much very little.But table 5 shows that the service life of the catalyst of all these method preparations is very long, good stability.
Embodiment 3
Adopt method similarly to Example 1 to prepare pure TiO
2Photochemical catalyst, difference are, digestion time time 0.5d and 4d, the pure TiO of Zhi Bei each with this understanding
2The part-structure parameter of photochemical catalyst is listed in table 6.
The structural parameters of the photochemical catalyst of different overcritical times of table 6
| Sample number into spectrum | Digestion time (d) | Sintering temperature (℃) | Specific area (cc/g) | Density (kg/m 3) |
| 550#-1 | 2 | 550 | 27 | 84 |
| 550#-4 | 0.5 | 550 | 26 | 87 |
| 550#-5 | 4 | 550 | 22 | 100 |
Above-mentioned catalyst is applied to the reaction of liquid phase phenol photocatalytic degradation, temperature 303.0K time 2h; The initial concentration of phenol is 0.1 grams per liter, volume 50mL; Catalyst amount 0.05 gram; Light source is three of 254nm, power averaging 8W).Result such as table 7, table 8.
The photochemical catalyst Pyrogentisinic Acid's of table 7 different ageing degraded
| Sample number into spectrum | Digestion time (d) | Degradation rate (2h) |
| 550#-1 | 2 | 99％ |
| 550#-4 | 0.5 | 98％ |
| 550#-5 | 4 | 90％ |
Table 8 catalyst is reused the relation of number of times and degradation rate
| Reaction times | Reaction time | Degradation rate (550#-1) | Degradation rate (550#-4) | Degradation rate (550#-5) |
| 1 | 2h | 99％ | 98％ | 90％ |
| 2 | 2h | 98％ | 97％ | 88％ |
| 3 | 2h | 98％ | 96％ | 88％ |
| 4 | 2h | 97％ | 96％ | 88％ |
| 5 | 2h | 96％ | 96％ | 87％ |
| 6 | 2h | 96％ | 95％ | 87％ |
| 7 | 2h | 96％ | 95％ | 87％ |
| 8 | 2h | 95％ | 95％ | 85％ |
By table 7 as seen in the too short or long activity of such catalysts that all is unfavorable for of digestion time.Table 8 shows that the time of ageing is influenced hardly to life of catalyst.
Embodiment 4
Adopt method similarly to Example 1 to prepare pure TiO
2Photochemical catalyst, difference are that used titanium source is positive four butyl esters of metatitanic acid, isopropyl titanate, the pure TiO of Zhi Bei each with this understanding
2The part-structure parameter of photochemical catalyst is listed in table 9.
The structural parameters of the photochemical catalyst of different overcritical times of table 9
| Sample number into spectrum | The titanium source | Sintering temperature (℃) | Specific area (cc/g) | Density (kg/m3) |
| 550#-1 | |
550 | 27 | 84 |
| 550#-6 | |
550 | 20 | 105 |
| 550#-7 | |
550 | 25 | 89 |
Above-mentioned catalyst is applied to the reaction of liquid phase phenol photocatalytic degradation, temperature 303.0K time 2h; The initial concentration of phenol is 0.1 grams per liter, volume 50mL; Catalyst amount 0.05 gram; Light source is three of 254nm, power averaging 8W).Result such as table 10, table 11:
The photochemical catalyst Pyrogentisinic Acid's of table 10 different ageing degraded
| Sample number into spectrum | The titanium source | Degradation rate (2h) |
| 550#-1 | Titanium tetrachloride | 99％ |
| 550#-6 | Butyl titanate | 94％ |
| 550#-7 | Isopropyl titanate | 96％ |
Table 11 catalyst is reused the relation of number of times and degradation rate
| Reaction times | Reaction time | Degradation rate (550#-1) | Degradation rate (550#-6) | Degradation rate (550#-7) |
| 1 | 2h | 99％ | 94％ | 96％ |
| 2 | 2h | 98％ | 92％ | 95％ |
| 3 | 2h | 98％ | 92％ | 94％ |
| 4 | 2h | 97％ | 91％ | 94％ |
| 5 | 2h | 96％ | 91％ | 94％ |
| 6 | 2h | 96％ | 90％ | 93％ |
| 7 | 2h | 96％ | 90％ | 91％ |
| 8 | 2h | 95％ | 90％ | 90％ |
Variation by the visible titanium source of table 10 does not have much influences to activity of such catalysts.Table 11 shows that the variation in titanium source is influenced hardly to life of catalyst.
Claims (3)
1, a kind of TiO
2The preparation method of photochemical catalyst may further comprise the steps:
(1) under the temperature of 278-313K, glycerine is slowly splashed in the absolute ethyl alcohol, fully stir, obtain solution A; The A colloidal sol that predecessor slowly splashes in the A solution and fully stirring 0.5-2h obtains homogeneous transparent with titanium; Wherein the volume ratio of the predecessor of titanium, glycerine and absolute ethyl alcohol is 0.5-2: 10: 20;
(2) ether is joined in the resulting A colloidal sol, continue to stir 10min-20min, get sol B; The volumn concentration that adds ether accounts for the 14%-40% of cumulative volume;
(3) sol B is transferred in the water heating kettle, ageing is 1 day-7 days under the 363-403K temperature, takes out and naturally cool to room temperature, and the taking-up white depositions is colourless to the ethanol washing lotion with ethanol washing several times, puts into 100 ℃ oven drying behind the suction filtration, obtains TiO
2Particulate;
(4) with TiO
2Particulate places Muffle furnace, is warming up to 623-973K roasting 180-600min with the programming rate of 2K/min, promptly makes TiO
2Photochemical catalyst;
The predecessor of above-mentioned titanium is selected from a kind of in titanium tetrachloride, butyl titanate, tetraethyl titanate or the isopropyl titanate.
2, a kind of TiO according to claim 1
2The preparation method of photochemical catalyst is characterized in that: the predecessor of described titanium is a titanium tetrachloride.
3, a kind of TiO according to claim 1
2The preparation method of photochemical catalyst is characterized in that: the digestion time of described (3) step is 2 days, and the ageing temperature is 382-384K.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100247724A CN100434178C (en) | 2006-03-16 | 2006-03-16 | Process for preparing titanium dioxide photo catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100247724A CN100434178C (en) | 2006-03-16 | 2006-03-16 | Process for preparing titanium dioxide photo catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1820852A CN1820852A (en) | 2006-08-23 |
| CN100434178C true CN100434178C (en) | 2008-11-19 |
Family
ID=36922516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100247724A Expired - Fee Related CN100434178C (en) | 2006-03-16 | 2006-03-16 | Process for preparing titanium dioxide photo catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100434178C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451717B (en) * | 2010-10-22 | 2013-06-19 | 中国科学院合肥物质科学研究院 | Titanium oxide micro-nanotube with visible-light catalysis effect, and preparation method thereof |
| CN104868112B (en) * | 2015-05-12 | 2017-06-20 | 吉林大学 | Carbon coating titanium dioxide nanoplate array and graphene combination electrode material and preparation method thereof |
| CN111375404B (en) * | 2020-04-17 | 2021-06-15 | 天津大学 | P-type titanium dioxide/n-type tungsten trioxide heterojunction catalyst, preparation method thereof and application thereof in photochemical synthesis of fuel |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846511A (en) * | 1995-06-19 | 1998-12-08 | Korea Advanced Institute Of Science And Technology | Process for preparing crystalline titania powders from a solution of titanium salt in a mixed solvent of water and alcohol |
| CN1337425A (en) * | 2001-08-31 | 2002-02-27 | 清华大学 | Prepn proces sof mesoporous TiO2 powder as photocatalyst by using polyglycol as additive |
| JP2002146283A (en) * | 2000-11-07 | 2002-05-22 | Taki Chem Co Ltd | Photocatalytic coating fluid containing titanium oxide and its manufacturing method and titanium oxide photocatalytic structure |
| CN1478725A (en) * | 2003-01-13 | 2004-03-03 | 复旦大学 | Preparation method of crystal phase controllable titanium dioxide nanometer crystal |
| CN1562462A (en) * | 2004-03-30 | 2005-01-12 | 中国科学院上海硅酸盐研究所 | Method for preparing photocatalysis powder of titainia with medium pores by using pore forming agent of glycerin |
| KR20050028723A (en) * | 2003-09-19 | 2005-03-23 | 주식회사 나노 | Method for producing titanium oxide particle and method for producing titanium oxide thin layer using the same |
| CN1686821A (en) * | 2005-05-23 | 2005-10-26 | 北京工业大学 | Method for preparing medium pore molecular sieve of titanium dioxide |
-
2006
- 2006-03-16 CN CNB2006100247724A patent/CN100434178C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846511A (en) * | 1995-06-19 | 1998-12-08 | Korea Advanced Institute Of Science And Technology | Process for preparing crystalline titania powders from a solution of titanium salt in a mixed solvent of water and alcohol |
| JP2002146283A (en) * | 2000-11-07 | 2002-05-22 | Taki Chem Co Ltd | Photocatalytic coating fluid containing titanium oxide and its manufacturing method and titanium oxide photocatalytic structure |
| CN1337425A (en) * | 2001-08-31 | 2002-02-27 | 清华大学 | Prepn proces sof mesoporous TiO2 powder as photocatalyst by using polyglycol as additive |
| CN1478725A (en) * | 2003-01-13 | 2004-03-03 | 复旦大学 | Preparation method of crystal phase controllable titanium dioxide nanometer crystal |
| KR20050028723A (en) * | 2003-09-19 | 2005-03-23 | 주식회사 나노 | Method for producing titanium oxide particle and method for producing titanium oxide thin layer using the same |
| CN1562462A (en) * | 2004-03-30 | 2005-01-12 | 中国科学院上海硅酸盐研究所 | Method for preparing photocatalysis powder of titainia with medium pores by using pore forming agent of glycerin |
| CN1686821A (en) * | 2005-05-23 | 2005-10-26 | 北京工业大学 | Method for preparing medium pore molecular sieve of titanium dioxide |
Non-Patent Citations (6)
| Title |
|---|
| Preparation of TiO2 nanoparticles in glycerol-containingsolutions. Tran Trung et al.Materials Letters,Vol.57 . 2003 |
| Preparation of TiO2 nanoparticles in glycerol-containingsolutions. Tran Trung et al.Materials Letters,Vol.57 . 2003 * |
| 丙三醇对水热法制备TiO2微粒粒径及分布的影响. 高龙柱等.合成技术及应用，第19卷第4期. 2004 |
| 丙三醇对水热法制备TiO2微粒粒径及分布的影响. 高龙柱等.合成技术及应用，第19卷第4期. 2004 * |
| 介孔TiO2粉体的合成和表征及光催化性能研究. 张维光等.化学研究与应用，第5期. 2005 |
| 介孔TiO2粉体的合成和表征及光催化性能研究. 张维光等.化学研究与应用，第5期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1820852A (en) | 2006-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6576589B1 (en) | Method for making anatase type titanium dioxide photocatalyst | |
| CN100494072C (en) | Method for producing nano-anatase mine titanium oxide water sol | |
| CN106268734B (en) | A kind of preparation method of water dispersible ternary mixed crystal nano titanium dioxide photocatalyst | |
| CN102335602B (en) | Bismuth tungstate composite photocatalyst, preparation method thereof, and application thereof | |
| CN101391811B (en) | Method for preparing high specific surface area titanic oxide | |
| CN101371981A (en) | Nano titanic oxide photocatalyst of high activity with phosphoric acid surface modification as well as synthetic method | |
| CN101508464B (en) | Process for preparing anatase type nano-titanium dioxide | |
| CN102600881B (en) | Preparation method for nitrogen and carbon co-doped nanometer titanium dioxide visible-light photocatalyst | |
| CN100551522C (en) | The method of producing interpose porus titanium dioxide photocatalyst by hydro-thermal method in weak acid condition | |
| CN101497038A (en) | Nano titanic oxide photocatalyst responding to visible light and preparation method thereof | |
| CN101318694A (en) | Method for preparing titanium dioxide nanocrystalline with highlight catalytic activity in low-temperature | |
| CN105597728A (en) | Titanium dioxide/bismuth titanate ultrasonic enhanced photocatalyst and preparation method thereof | |
| CN107126944A (en) | A kind of many doping titanium dioxide nano particles of many defects with high visible light catalytic activity and preparation method | |
| CN105903486A (en) | Z-type photocatalyst and preparation method thereof | |
| CN104801328A (en) | Method for preparing TiO2/g-C3N4 composite photocatalyst at low temperature | |
| CN105543961A (en) | Nano TiO2 monocrystalline material, preparation method therefor and use of nano TiO2 monocrystalline material | |
| CN103170333A (en) | Method for preparing recyclable magnetic titanium dioxide nanometer photocatalyst | |
| CN107522169A (en) | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide | |
| CN109331817A (en) | It is a kind of for decomposing the catalysis material and preparation method of organic matter in air | |
| CN100434178C (en) | Process for preparing titanium dioxide photo catalyst | |
| CN103274461A (en) | Method for modulating titanium dioxide crystalline phases by using fluoride ions | |
| CN103657628B (en) | A kind of SnO 2-TiO 2the preparation method of compound nanometer photocatalyst | |
| CN102995120B (en) | Nanometer TiO2 monocrystalline material, preparation method and application thereof | |
| CN101214999A (en) | Method for preparing doping titanium dioxide nano crystal | |
| CN103601239A (en) | Preparation method of anatase and brookite mixed crystal TiO2 nanowire |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081119 Termination date: 20130316 |