CN101564694A - Method for preparing nitrogen doped nanometer titanium dioxide visible light photocatalyst - Google Patents
Method for preparing nitrogen doped nanometer titanium dioxide visible light photocatalyst Download PDFInfo
- Publication number
- CN101564694A CN101564694A CNA200810104972XA CN200810104972A CN101564694A CN 101564694 A CN101564694 A CN 101564694A CN A200810104972X A CNA200810104972X A CN A200810104972XA CN 200810104972 A CN200810104972 A CN 200810104972A CN 101564694 A CN101564694 A CN 101564694A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- visible light
- nitrogen
- nanometer titanium
- light photocatalyst
- 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.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a method for preparing a nitrogen doped nanometer titanium dioxide visible light photocatalyst and belongs to the field of titanium dioxide photocatalysis. The invention aims to solve the problem of low catalytic activity and the collapse of porous channels in the preparation process in the prior catalyst. The method comprises the followings steps that: 1), inorganic titanate reacts with a nitrogen containing compound in the presence of a surfactant to generate a sediment, the reaction solution is stirred for 0.5 to 10h and then stood and aged for 0 to 48h; 2), the sediment is subjected to vacuum freeze drying to form a precursor of the nanometer titanium dioxide visible light photocatalyst; and 3), the precursor is calcined at a temperature of between 250 and 800 DEG C for 0.5 to 10h to form the nitrogen doped nanometer titanium dioxide visible light photocatalyst. The method can avoid the collapse of the porous channels, and the prepared catalyst has the advantages of high number of surface active sites, big specific surface area, high catalytic activity, and the like.
Description
Technical field
The invention belongs to field of titanium dioxide photocatalysis, be specifically related to a kind of preparation method of nitrogen doped nanometer titanium dioxide visible light photocatalyst.
Background technology
Utilize TiO from Fujishima in 1972 and Honda report
2Monocrystalline electrode photodissociation water (Fujishima A.Honda K.Electrochemical photolysis of waterata semiconductor elect rode.[J] .Nature, 1972,238:37-38.) since, people are to semiconductor light-catalyst TiO
2Big quantity research has been carried out in application.TiO
2All demonstrate good development prospect at aspects such as wastewater treatment, air cleaning, photochemical cell, water electrolysis hydrogen productions.As far back as 1977, Frank and Bard just began to attempt using TiO
2Cyanide in the degradation water (J.Am.Chem.Soc.99 (1977) 303. for S.N.Frank, A.J.Bard), TiO2 has caused the very big interest of people in the application of environmental area since then.After the nineties, the high speed development of the serious day by day and nanometer technology of preparing of global problem of environmental pollution is with nano-TiO
2The surround lighting catalyticing research that photochemical catalyst is attached most importance to becomes one of focus of researchs such as material, catalytic chemistry and environmental science.
But TiO
2Energy gap be 3.2eV, bigger, make the ultraviolet light have only wavelength to be equal to or less than 387.5nm just can make it to excite the demonstration catalytic activity, therefore very low to the utilization rate of sunshine; Light induced electron and photohole is compound easily on the other hand, and its optical efficiency is reduced greatly.The researcher mainly adopts Technique on T iO such as doping metals, photoactivate, finishing both at home and abroad
2Carry out modification, to increase photocatalysis respective range and optical efficiency.
Calendar year 2001 Asahi adopts TiO
2Obtain nitrogen doped Ti O with the nitrogen reaction
2, this material character is stable, and can respond under the visible light condition.Now, lot of documents shows all that nitrogen is doped with to be beneficial to and increases TiO
2The photoresponse scope.But the increase of this response range is to be based upon on the active basis that reduces of ultraviolet catalytic on the one hand, and the photoresponse scope increases, and shows that the energy gap between photochemical catalyst valence band and the conduction band reduces, thereby the oxidisability of photohole reduces.On the other hand, at present the photochemical catalyst cost for wastewater treatment of bibliographical information is too high, show mainly that the power of light source is excessive, degradation product is single and waste strength cross low on.The real industrialization that therefore will realize photocatalysis treatment of waste water need increase TiO when increasing photoresponse
2Photocatalytic activity, reduce cost for wastewater treatment.
Find that by literature search publication number is the different preparation methods that the Chinese patent of CN1557540, CN1903436, CN1565721, CN1555913, CN1736584 has been reported nitrogen-doped titanium dioxide respectively.But preparation method's baking temperature of above-mentioned patent disclosure is all than higher, the water or other alcohols material that have a large amount of liquid conditions between the duct of titaniferous precipitation, because the warp tension ratio between the liquid surface is bigger, in dry run, along with evaporation of water, the duct of precipitation subsides easily, causes the specific area of last catalyst to descend, reduce the catalyst surface active position, and catalytic activity reduces.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, and provide a kind of specific area and active sites quantity big, effectively prevent the preparation method of the nitrogen doped nanometer titanium dioxide visible light photocatalyst that the duct subsides in the dry run.
The preparation method of a kind of nitrogen doped nanometer titanium dioxide visible light photocatalyst provided by the present invention comprises the steps:
1) the configuration inorganic titanate aqueous solution, titanium ion concentration is 0.01～10mol/L in the solution;
2) in the inorganic titanate aqueous solution of step 1) preparation, add surfactant, the addition of surfactant is 0.1～1% of an inorganic titanate aqueous solution weight, back adding nitrogen-containing compound stirs, make inorganic titanate precipitate (promptly getting catalyst precursor) fully, after continuing to stir 0.5～10h, still aging 0～48h;
3) adopt deionized water washing step 2) in precipitation, the anion total concentration is lower than 0.1mol/L to the cleaning solution, after will precipitate cooling again it being solidified, is not higher than 0.5 atmospheric pressure in vacuum, is lower than drying under the condition of freezing point of water;
Adopting the principle of vacuum-freezing process drying is under vacuum state, utilizes the distillation principle, makes the moisture content in the material that freezes in advance, without the thawing of ice, is that water vapour is removed with the distillation of ice attitude directly, thereby makes dry materials.Catalyst precursor is under freezing condition, and surface tension is very little, can prevent catalyst the subsiding of duct in drying, increases specific area.Because catalyst precursor molecule under freezing condition moves difficulty, therefore can make the molecular distribution state of the catalyst precursor that obtains after the drying identical simultaneously, can effectively prevent the change of structure in the dry run with dry preceding state.
4) be deposited in 250～800 ℃ with dried in the step 3), calcining 0.5～10h makes nitrogen doped nanometer titanium dioxide visible light photocatalyst.
Wherein, the inorganic titanate described in the step 1) is selected from one or more in titanium tetrachloride, titanyl sulfate or the titanium sulfate; Step 2) surfactant described in is selected from one or more in diethanol amine, triethanolamine, AEO (AE03), neopelex, odium stearate, lauryl sodium sulfate, tween, polyethylene glycol, the oleic acid; Step 2) nitrogen-containing compound described in is selected from one or more in ammoniacal liquor, carbonic hydroammonium or the ammonia.
Compare with the existing method for preparing the nitrogen-doped nanometer titanium dioxide photochemical catalyst, the present invention has the following advantages:
1) the present invention adopts the vacuum-freezing process drying, can prevent subsiding of duct when drying, thereby effectively increase specific area.
2) volume when being solidified by liquid of the water between the precipitation duct increases, and can increase channel diameter greatly, thereby can effectively improve the quantity of surface-active position.
Be in solid state when 3) dry, molecular migration is difficulty very, thereby dried precipitation structure is identical can keep dry with it the time, can prevent the change of catalyst structure greatly, thereby guarantee the high activity of catalyst.
Description of drawings
The XRD spectra of the nitrogen doped nanometer titanium dioxide visible light photocatalyst of Fig. 1, embodiment 1 preparation
The N of the nitrogen doped nanometer titanium dioxide visible light photocatalyst of Fig. 2, embodiment 2 preparations
1sSpectrogram (surface light electron spectrum)
The uv drs spectrogram of the nitrogen doped nanometer titanium dioxide visible light photocatalyst of Fig. 3, embodiment 3 preparations
The specific embodiment
Embodiment 1
1) titanium sulfate solution of configuration 0.01mol/L adds the surfactant triethanolamine under stirring condition, the quality of surfactant accounts for 0.1% of titanium sulfate solution quality, the ammoniacal liquor that adds 1mol/L after stirring, titanium sulfate is precipitated fully, continue to stir 0.5h, still aging 20h;
2) with step 2) in precipitation adopt that the anion total concentration is lower than 0.1mol/L in the water of deionized water washing to the washing, will be deposited in pressure then is below the 1000Pa, temperature is lower than vacuum drying in-10 ℃ the environment;
3) wait to precipitate bone dry after, be heated 450 ℃ the calcining 1.5h, promptly make the nitrogen-doped nanometer titanium dioxide photochemical catalyst.Color sample is light yellow, is designated as the 1# sample.
Adopt XRD to detect its structure in the 1# sample, sample is the anatase titanium dioxide nitrogen-doped nanometer titanium dioxide, as shown in Figure 1.
Embodiment 2
1) titanium sulfate solution of configuration 1mol/L, add the surfactant tween under stirring condition, it is 0.2% of titanium sulfate solution quality that tween adds quality, and the ammoniacal liquor that the back that stirs adds 5mol/L precipitates titanium sulfate fully, continue to stir 2h, still aging 10h;
2) will precipitate and adopt that all anion total concentrations are lower than 0.1mol/L in the water of deionized water washing to the washing, will precipitate as for pressure then is below the 800Pa, and temperature is lower than vacuum drying in-5 ℃ the environment;
3) wait to precipitate bone dry after, be heated 800 ℃ the calcining 0.5h, promptly make nitrogen-doped titanium dioxide photocatalyst.Color sample is single yellow, is designated as the 2# sample.
Adopt XPS to detect its structure in the 2# sample, the result shows that the N doping has entered TiO
2Lattice in.
Embodiment 3
1) titanium tetrachloride solution of configuration 10mol/L, under stirring condition, add surfactant polyethylene, the surfactant quality accounts for 0.3% of titanium tetrachloride solution gross mass, the ammonium bicarbonate aqueous solution that adds 2mol/L after stirring precipitates titanium tetrachloride fully, continue to stir 2h, still aging 24h;
2) will precipitate and adopt that all anion total concentrations are lower than 0.1mol/L in the water of deionized water washing to the washing, will precipitate as for pressure then is below the 200Pa, and temperature is lower than vacuum drying in-30 ℃ the environment;
3) wait to precipitate bone dry after, be heated 500 ℃ the calcining 1h, promptly make nitrogen-doped titanium dioxide photocatalyst.Color sample is a glassy yellow, is designated as the 3# sample.
The 3# sample adopts the UV, visible light diffuse reflection to detect its spectrum property, and the absorption of sample wavelength can expand to 570nm.
Embodiment 4
1) titanyl sulfate solution of configuration 0.25mol/L, under stirring condition, add the surfactant neopelex, the neopelex quality accounts for 0.3% of titanium sulfate solution gross mass, the ammoniacal liquor that adds 3mol/L after stirring precipitates titanyl sulfate fully, continue to stir 0.5h, still aging 15h;
2) will precipitate and adopt that all anion total concentrations are lower than 0.1mol/L in the water of deionized water washing to the washing,
To precipitate as for pressure then is below the 250Pa, and temperature is lower than vacuum drying in-25 ℃ the environment;
3) wait to precipitate bone dry after, be heated 500 ℃ the calcining 3h, promptly make nitrogen-doped titanium dioxide photocatalyst.Color sample is yellow, is designated as the 4# sample.
4# adopts and degrades under the condition of visible light, and 6h can be degraded to 67ppm with the acrylic acid wastewater of 1000ppm, reaches discharging standards.
Embodiment 5
1) titanyl sulfate solution of configuration 0.3mol/L, under stirring condition, add the surfactant AEO, the AEO quality accounts for 0.2% of titanium sulfate solution gross mass, the ammoniacal liquor that adds 2mol/L after stirring precipitates titanyl sulfate fully, continue to stir 10h, still aging 0h;
2) will precipitate and adopt the Shui Zhongshui long anion total concentration of deionized water washing to the washing to be lower than 0.05mol/L, will precipitate as for pressure then is below the 150Pa, and temperature is lower than vacuum drying in-15 ℃ the environment;
3) wait to precipitate bone dry after, be heated 600 ℃ the calcining 1h, promptly make nitrogen-doped titanium dioxide photocatalyst.Color sample is a buff, is designated as the 5# sample.
5# adopts and degrades under the condition of sunshine, and 5h can be degraded to 92ppm with the dyeing waste water of 1000ppm, reaches discharging standards.
Embodiment 6
1) titanyl sulfate solution of configuration 5mol/L adds surfactant oleic acid under stirring condition, the oleic acid quality accounts for 1% of titanium sulfate solution gross mass, and the back that stirs feeds ammonia, titanyl sulfate is precipitated fully, mixing time 0.5h, still aging 48h;
2) will precipitate and adopt that all anion concentrations always are lower than 0.05mol/L in the water of deionized water washing to the washing, will precipitate as for pressure then is below the 150Pa, and temperature is lower than vacuum drying in-15 ℃ the environment;
3) wait to precipitate bone dry after, be heated 250 ℃ the calcining 10h, promptly make nitrogen-doped titanium dioxide photocatalyst.Color sample is a buff, is designated as the 6# sample.
6# adopts and degrades under the condition of sunshine, and 10h can be degraded to 85ppm with the dyeing waste water of 1000ppm, reaches discharging standards.
Claims (4)
1, a kind of preparation method of nitrogen doped nanometer titanium dioxide visible light photocatalyst is characterized in that, comprises the steps:
1) the configuration inorganic titanate aqueous solution, titanium ion concentration is 0.01～10mol/L in the solution;
2) in the inorganic titanate aqueous solution of step 1) preparation, add surfactant, the addition of surfactant is 0.1～1% of an inorganic titanate aqueous solution weight, back adding nitrogen-containing compound stirs, inorganic titanate is precipitated fully, after continuing to stir 0.5～10h, still aging 0～48h;
3) adopt deionized water washing step 2) in precipitation, the anion total concentration is lower than 0.1mol/L to the cleaning solution, after will precipitate cooling again it being solidified, is not higher than 0.5 atmospheric pressure in vacuum, is lower than drying under the condition of freezing point of water;
4) be deposited in 250～800 ℃ with dried in the step 3), calcining 0.5～10h makes nitrogen doped nanometer titanium dioxide visible light photocatalyst.
2, method according to claim 1 is characterized in that, the inorganic titanate thing described in the step 1) is selected from one or more in titanium tetrachloride, titanyl sulfate or the titanium sulfate.
3, method according to claim 1, it is characterized in that step 2) described in surfactant be selected from diethanol amine, triethanolamine, AEO, neopelex, odium stearate, lauryl sodium sulfate, tween, polyethylene glycol, the oleic acid one or more.
4, method according to claim 1 is characterized in that step 2) described in nitrogen-containing compound be selected from ammoniacal liquor, carbonic hydroammonium or the ammonia one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810104972XA CN101564694B (en) | 2008-04-25 | 2008-04-25 | Method for preparing nitrogen doped nanometer titanium dioxide visible light photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810104972XA CN101564694B (en) | 2008-04-25 | 2008-04-25 | Method for preparing nitrogen doped nanometer titanium dioxide visible light photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101564694A true CN101564694A (en) | 2009-10-28 |
| CN101564694B CN101564694B (en) | 2011-05-11 |
Family
ID=41281162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810104972XA Expired - Fee Related CN101564694B (en) | 2008-04-25 | 2008-04-25 | Method for preparing nitrogen doped nanometer titanium dioxide visible light photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101564694B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423809A (en) * | 2011-12-07 | 2012-04-25 | 南京大学 | Method for preparing PtV or PtCr alloy nanoparticles |
| CN104785282A (en) * | 2015-01-29 | 2015-07-22 | 华东理工大学 | New type trivalent titanium and nonmetallic element nitrogen co-doped titanium dioxide nano photocatalyst preparation |
| CN105191981A (en) * | 2015-10-09 | 2015-12-30 | 塔里木大学 | Preparation method for copper-doped nanometer titania with photo-catalysis antibacterial property |
| CZ305801B6 (en) * | 2011-07-18 | 2016-03-23 | Ústav Anorganické Chemie Av Čr, V.V.I. | Process for preparing photocatalycally active material with foamy structure |
| CN106320094A (en) * | 2016-09-13 | 2017-01-11 | 福建农林大学 | PVC (polyvinyl chloride) wallpaper with function of photocatalytically degrading formaldehyde in visible light and method for preparing PVC wallpaper |
| CN106492780A (en) * | 2016-12-13 | 2017-03-15 | 富思特新材料科技发展股份有限公司 | A kind of preparation method of visible-light photocatalyst pucherite |
| CN107694596A (en) * | 2017-10-24 | 2018-02-16 | 宝鸡圭彬光电设备有限公司 | A kind of preparation method of titanium dioxide optical catalyst |
| CN109160539A (en) * | 2018-11-12 | 2019-01-08 | 青岛科技大学 | A kind of nano-titanium dioxide and preparation method thereof |
| CN109694115A (en) * | 2019-01-25 | 2019-04-30 | 清华大学合肥公共安全研究院 | A method of black and odorous water is administered using sunlight |
| CN113318720A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst and preparation method and application thereof |
| CN113636596A (en) * | 2021-07-01 | 2021-11-12 | 深圳市银宝山新科技股份有限公司 | Preparation method of nano titanium dioxide photocatalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506154A (en) * | 2002-12-06 | 2004-06-23 | 中国科学院化学研究所 | Prepn of nitrogen-doped titania powder |
| CN1267186C (en) * | 2003-07-03 | 2006-08-02 | 中国科学院化学研究所 | Method for preparing nitrogen doped titania visible light catalyzer |
-
2008
- 2008-04-25 CN CN200810104972XA patent/CN101564694B/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ305801B6 (en) * | 2011-07-18 | 2016-03-23 | Ústav Anorganické Chemie Av Čr, V.V.I. | Process for preparing photocatalycally active material with foamy structure |
| CN102423809A (en) * | 2011-12-07 | 2012-04-25 | 南京大学 | Method for preparing PtV or PtCr alloy nanoparticles |
| CN102423809B (en) * | 2011-12-07 | 2013-11-20 | 南京大学 | Method for preparing PtV or PtCr alloy nanoparticles |
| CN104785282A (en) * | 2015-01-29 | 2015-07-22 | 华东理工大学 | New type trivalent titanium and nonmetallic element nitrogen co-doped titanium dioxide nano photocatalyst preparation |
| CN105191981A (en) * | 2015-10-09 | 2015-12-30 | 塔里木大学 | Preparation method for copper-doped nanometer titania with photo-catalysis antibacterial property |
| CN106320094B (en) * | 2016-09-13 | 2019-01-22 | 福建农林大学 | A kind of PVC wallpaper and preparation method thereof of visible light photocatalytic degradation formaldehyde |
| CN106320094A (en) * | 2016-09-13 | 2017-01-11 | 福建农林大学 | PVC (polyvinyl chloride) wallpaper with function of photocatalytically degrading formaldehyde in visible light and method for preparing PVC wallpaper |
| CN106492780A (en) * | 2016-12-13 | 2017-03-15 | 富思特新材料科技发展股份有限公司 | A kind of preparation method of visible-light photocatalyst pucherite |
| CN106492780B (en) * | 2016-12-13 | 2019-06-11 | 富思特新材料科技发展股份有限公司 | A kind of preparation method of visible-light photocatalyst pucherite |
| CN107694596A (en) * | 2017-10-24 | 2018-02-16 | 宝鸡圭彬光电设备有限公司 | A kind of preparation method of titanium dioxide optical catalyst |
| CN109160539A (en) * | 2018-11-12 | 2019-01-08 | 青岛科技大学 | A kind of nano-titanium dioxide and preparation method thereof |
| CN109694115A (en) * | 2019-01-25 | 2019-04-30 | 清华大学合肥公共安全研究院 | A method of black and odorous water is administered using sunlight |
| CN113318720A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst and preparation method and application thereof |
| CN113318720B (en) * | 2020-02-28 | 2023-12-29 | 中科粤能净(山东)新材料有限公司 | Photocatalyst, and preparation method and application thereof |
| CN113636596A (en) * | 2021-07-01 | 2021-11-12 | 深圳市银宝山新科技股份有限公司 | Preparation method of nano titanium dioxide photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101564694B (en) | 2011-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101564694B (en) | Method for preparing nitrogen doped nanometer titanium dioxide visible light photocatalyst | |
| Ke et al. | Nanostructured ternary metal tungstate-based photocatalysts for environmental purification and solar water splitting: a review | |
| CN100375650C (en) | Low temperature process of preparing carbon-doped mesoporous TiO2 visible light catalyst | |
| CN102949991B (en) | Method for preparing BiVO4 film with photocatalysis performance by using sol-gel method | |
| CN103506142B (en) | A kind of Molybdenum disulfide/silver phosphate composite visible light photocatalytic material and preparation method thereof | |
| CN103191725B (en) | BiVO4/Bi2WO6 composite semiconductor material as well as hydrothermal preparation method and application thereof | |
| CN103240073B (en) | Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof | |
| CN101722015B (en) | Method for preparing super-strong acidified doped nano-TiO2 photocatalyst | |
| CN104525186A (en) | Spherical bismuth molybdate nanocomposite having heterostructure as well as preparation method and application of nanocomposite | |
| CN104971761A (en) | Nitrogen/sulfur-doped bismuth oxyhalide visible light catalysis material and preparation method thereof | |
| CN106917128A (en) | A kind of tin molybdenum codope titanium dioxide nanotube array electrode and preparation method | |
| CN108906020A (en) | A kind of preparation method of titanium dioxide-zinc oxide composite catalyzing material | |
| CN102125831B (en) | Method for preparing mesoporous Bi2O3/TiO2 nano photocatalyst | |
| CN102513043A (en) | Preparation method of nitrogen (N)-doped titanium dioxide (TiO2) microspheres | |
| CN109046313A (en) | A kind of preparation method and application of high activity cerium dioxide photocatalyst | |
| CN102173450A (en) | Preparation method of titanium dioxide film | |
| CN104511280A (en) | Visible-light-induced photocatalyst and preparation method thereof | |
| CN109012697A (en) | A kind of sunlight all band TiO2/VS4The preparation method of photochemical catalyst | |
| CN105233821A (en) | Strontium-doped and silver-doped nanometer titanium dioxide visible light catalyst | |
| CN102659178A (en) | Synthesis technology for visible light titanium dioxide nanosheet with exposed {001} face and oxygen defects | |
| Gao et al. | Oxygen vacancy engineering of titania-induced by Sr2+ dopants for visible-light-driven hydrogen evolution | |
| CN104857942A (en) | Cadmium sulfide sensitization hydrogenation branched titanium dioxide nanorod array membrane and light catalyst | |
| CN102553626A (en) | Preparation method of carbon-nitrogen-codoped TiO2 nano catalysis material | |
| CN102179260B (en) | Multi-component doped photocatalytic material and preparation method thereof | |
| CN104353449A (en) | Preparation method of graphene/bismuth titanate photocatalytic material |
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: 20110511 Termination date: 20130425 |