CN102653416B - Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking - Google Patents
Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking Download PDFInfo
- Publication number
- CN102653416B CN102653416B CN201110048647.8A CN201110048647A CN102653416B CN 102653416 B CN102653416 B CN 102653416B CN 201110048647 A CN201110048647 A CN 201110048647A CN 102653416 B CN102653416 B CN 102653416B
- Authority
- CN
- China
- Prior art keywords
- sample
- titanium dioxide
- titanium dichloride
- deionized water
- hydro
- 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
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparing titanium dioxide nanospheres by titanocene dichloride cracking, which comprises the following steps: dissolving titanocene dichloride in deionized water, dropwisely adding ethylenediamine, performing ultrasonic vibration and a hydrothermal reaction, then drying, putting the sample in a porcelain boat, heating to 400-500 DEG C in a tubular furnace with a controlled heating speed of 5-10 DEG C/min, performing heat preservation and reaction for 2 hours to obtain the product. Compared with the prior art, the invention greatly reduces cost, causes no pollution to the environment, adopts a simple hydro-thermal process, has mild conditions which are easy to be realized, and is convenient for industrial production; the invention can prepare a flower-like superstructure which is assembled by nanostructures; by controlling different temperatures and time, structures with various morphologies can be obtained; the product has good performance of photocatalytic degradation of organic matter in water, and has important applications in the environmental protection field in the future.
Description
Technical field
The invention belongs to technical field of nano material, especially relate to a kind of cyclopentadienyl titanium dichloride cracking that utilizes for the method for titanium dioxide nano-sphere.
Background technology
As far back as nineteen fifty-five, document has just been reported the synthetic of cyclopentadienyl titanium dichloride; Hartmunt Koepf in 1979 and Keopf-Maier find that it has certain anti-cancer properties.As a kind of novel organo-metallic cancer therapy drug, cyclopentadienyl titanium dichloride anticancer spectrum is wide, drug effect is high, toxicity is far below cis-platinum, and solid tumor is had to very strong restraining effect.In addition, cyclopentadienyl titanium dichloride is a kind of highly effective hydrogenation catalyzer, is widely used in olefinic polymerization and hydrogenation reaction.Such as, at high temperature cyclopentadienyl titanium dichloride is subject to illumination to cause tolane polymerization, obtains degree of crystallinity and be 95% poly-tolane.
Titanium dioxide common are Anatase and Rutile Type.3.0ev when wherein Rutile Type obtains band gap, and 3.2ev during Anatase band gap.Wherein nano level red schorl phase titanium dioxide has very high stability, granular superfine because of it, and surfactivity is high, in a lot of fields as fine ceramics, high-grade paint, sun care preparations have utmost point purposes widely.And nano level anatase octahedrite has higher photocatalytic activity, be usually used in catalytic decomposition, the photovoltaic cell field of organic decomposition mineralising, water in sewage.
Zeng You seminar report is prepared TiC material with chemical Vapor deposition process before this, be subject to this inspire the present invention by hydro-thermal legal system for the nanometer titanic oxide material that goes out metamict.Through differing temps roasting, amorphous state can be converted into anatase octahedrite and Rutile Type as required.Photocatalytic degradation rhodamine B, methylene blue solution experiments show, prepared anatase phase titanium dioxide has stronger photo-catalysis capability.
Summary of the invention
Object of the present invention be exactly in order to overcome the defect that above-mentioned prior art exists, provide that a kind of cost is lower, technique simple, mild condition, be easy to realize utilize cyclopentadienyl titanium dichloride cracking for the method for titanium dioxide nano-sphere.
Object of the present invention can be achieved through the following technical solutions:
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, it is characterized in that, the method comprises the following steps:
(1) accurately take cyclopentadienyl titanium dichloride and be dissolved in deionized water, controlled concentration is 2mg/ml, drips wherein quadrol under stirring, and the pH value of controlling solution is 9, by solution through ultrasonic oscillation 10-15min;
(2) above-mentioned solution is proceeded in polytetrafluoro hydrothermal reaction kettle inner bag, with stainless steel outer sleeve encapsulation, be placed in baking oven, controlling temperature is 120-160 ℃ of insulation 1-24h;
(3) above-mentioned hydro-thermal reaction naturally cools to room temperature after finishing, and then with deionized water, dehydrated alcohol, distinguishes centrifuge washing sample 3 times, and gained sample is through oven for drying;
(4) sample of oven dry is put into porcelain boat, controlling temperature rise rate is 5-10 ℃/min, is warmed up to 400-500 ℃ in tube furnace, and insulation reaction 2h, obtains product.
In described centrifuge washing, the rotating speed of whizzer is 1500-3000rpm.
Compared with prior art, the present invention has the following advantages:
(1) because the present invention's reaction does not need with an organic solvent, the solvent relating to only has water, can greatly reduce the cost that this is prepared on the one hand, on the other hand environment is not polluted yet, and meets international environment and requires trend;
(2) involved in the present invention to simple, the mild condition of hydro-thermal technique be easy to realize, be convenient to suitability for industrialized production;
(3) the prepared product of the present invention has organic performance in good photocatalytic degradation water, may have important application at field of Environment Protection in the future;
(4) by present method, can prepare a kind of superstructure that has nanostructure assembling with flower-like structure, control different temperature, time and obtain the different structure of pattern.
Accompanying drawing explanation
Fig. 1 is the SEM of gained sample figure after hydro-thermal in embodiment 1;
Fig. 2 is the SEM of gained sample figure after hydro-thermal in embodiment 2;
Fig. 3 is the SEM of gained sample figure after hydro-thermal in embodiment 3;
Fig. 4 is the XRD figure of gained sample after hydro-thermal in embodiment 1～3;
Fig. 5 is the SEM of gained sample figure after hydro-thermal in embodiment 4;
Fig. 6 is the SEM of gained sample figure after hydro-thermal in embodiment 5;
Fig. 7 is the SEM of gained sample figure after hydro-thermal in embodiment 6;
Fig. 8 is the SEM of gained sample figure after hydro-thermal in embodiment 7;
Fig. 9 is the XRD figure of gained sample after hydro-thermal in embodiment 4～7;
Figure 10 is the SEM figure of embodiment 1 hydro-thermal product gained sample after 400 ℃ of roastings;
Figure 11 is the SEM figure of embodiment 1 hydro-thermal product gained sample after 500 ℃ of roastings;
Figure 12 is embodiment 1 hydro-thermal product product XRD figure after 400 ℃, 500 ℃ roastings respectively;
Figure 13 is the degradation of methylene blue uv absorption spectra under UV-irradiation of gained sample after embodiment 1 hydro-thermal product roasting.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately weigh cyclopentadienyl titanium dichloride 20mg, put into the polytetrafluoroethylliner liner of 20ml capacity, add deionized water 10ml, 2 of quadrols, controlling pH value is 9.
(2) the above-mentioned mixed solution polytetrafluoroethylliner liner of having put is put into the ultrasonic 10min of ultrasonic apparatus, proceed in stainless steel still, sealing.
(3) the stainless steel still of good seal is put into baking oven, carries out hydro-thermal reaction, is warmed up to 120 ℃ in half an hour, is incubated 6 hours.Naturally cool to room temperature, after hydro-thermal, as shown in Figure 1, XRD figure picture as shown in Figure 4 for the SEM photo of gained sample.
(4) with glue head dropper, reaction product is sucked in centrifuge tube, with the speed centrifugation of 1500-2000 rev/min, the time is 5 minutes.Gained precipitate with deionized water and dehydrated alcohol difference centrifuge washing 3 times, dry in 80 ℃ of baking ovens.Obtain required sample.
(5) products obtained therefrom in tube furnace under air atmosphere with 5-10 ℃/min temperature rise rate, in tube furnace, be warmed up to 400-500 ℃, be incubated 2 hours.Obtain the good titanium dioxide of degree of crystallinity, after 400 ℃ of roastings, as shown in figure 10, after 500 ℃ of roastings, as shown in figure 11, after 400 ℃ and 500 ℃ of roastings, product XRD figure picture as shown in figure 12 for the SEM photo of gained sample for the SEM photo of gained sample.
(6) be used in the sample of 400 ℃ of roasting temperatures, degradation of methylene blue under UV-irradiation, uv absorption spectra is as shown in figure 13.
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately weigh cyclopentadienyl titanium dichloride 20mg, put into the polytetrafluoroethylliner liner of 20ml capacity.Add deionized water 10ml, 2 of triethylamines, controlling pH value is 9.
(2) the above-mentioned mixed solution polytetrafluoroethylliner liner of having put is put into the ultrasonic 10min of ultrasonic apparatus, proceed in stainless steel still, sealing.
(3) the stainless steel still of good seal is put into baking oven, carries out hydro-thermal reaction, is warmed up to 140 ℃ in half an hour, is incubated 6 hours.Naturally cool to room temperature, after hydro-thermal, as shown in Figure 2, XRD figure picture as shown in Figure 4 for the SEM photo of gained sample.
(4) with glue head dropper, reaction product is sucked in centrifuge tube, with the speed centrifugation of 1500-2000 rev/min, the time is 5 minutes.Gained precipitate with deionized water and dehydrated alcohol difference centrifuge washing 3 times, dry in 80 ℃ of baking ovens.Obtain required sample.
Embodiment 3
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately weigh cyclopentadienyl titanium dichloride 20mg, put into the polytetrafluoroethylliner liner of 20ml capacity.Add deionized water 10ml, 2 of thanomins, controlling pH value is 9.
(2) the above-mentioned mixed solution polytetrafluoroethylliner liner of having put is put into the ultrasonic 10min of ultrasonic apparatus, proceed in stainless steel still, sealing.
(3) the stainless steel still of good seal is put into baking oven, carries out hydro-thermal reaction, is warmed up to 160 ℃ in half an hour, is incubated 6 hours.Naturally cool to room temperature, after hydro-thermal, as shown in Figure 3, XRD figure picture as shown in Figure 4 for the SEM photo of gained sample.
(4) with glue head dropper, reaction product is sucked in centrifuge tube, with the speed centrifugation of 1500-2000 rev/min, the time is 5 minutes.Gained precipitate with deionized water and dehydrated alcohol difference centrifuge washing 3 times, dry in 80 ℃ of baking ovens.Obtain required sample.
Embodiment 4
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately weigh cyclopentadienyl titanium dichloride 20mg, put into the polytetrafluoroethylliner liner of 20ml capacity.Add deionized water 10ml, 2 of quadrols, controlling pH value is 9.
(2) the above-mentioned mixed solution polytetrafluoroethylliner liner of having put is put into the ultrasonic 10min of ultrasonic apparatus, proceed in stainless steel still, sealing.
(3) the stainless steel still of good seal is put into baking oven, carries out hydro-thermal reaction, is warmed up to 120 ℃ in half an hour, is incubated 3 hours.Naturally cool to room temperature, after hydro-thermal, as shown in Figure 5, XRD figure picture as shown in Figure 9 for the SEM photo of gained sample.
(4) with glue head dropper, reaction product is sucked in centrifuge tube, with the speed centrifugation of 1500-2000 rev/min, the time is 5 minutes.Gained precipitate with deionized water and dehydrated alcohol difference centrifuge washing 3 times, dry in 80 ℃ of baking ovens.Obtain required sample.
Embodiment 5
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately weigh cyclopentadienyl titanium dichloride 20mg, put into the polytetrafluoroethylliner liner of 20ml capacity.Add deionized water 10ml, 2 of quadrols, controlling pH value is 9.
(2) the above-mentioned mixed solution polytetrafluoroethylliner liner of having put is put into the ultrasonic 10min of ultrasonic apparatus, proceed in stainless steel still, sealing.
(3) the stainless steel still of good seal is put into baking oven, carries out hydro-thermal reaction, is warmed up to 120 ℃ in half an hour, is incubated 12 hours.Naturally cool to room temperature, after hydro-thermal, as shown in Figure 6, XRD figure picture as shown in Figure 9 for the SEM photo of gained sample.
(4) with glue head dropper, reaction product is sucked in centrifuge tube, with the speed centrifugation of 1500-2000 rev/min, the time is 5 minutes.Gained precipitate with deionized water and dehydrated alcohol difference centrifuge washing 3 times, dry in 80 ℃ of baking ovens.Obtain required sample.
Embodiment 6
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately weigh cyclopentadienyl titanium dichloride 20mg, put into the polytetrafluoroethylliner liner of 20ml capacity.Add deionized water 10ml, 2 of quadrols, controlling pH value is 9.
(2) the above-mentioned mixed solution polytetrafluoroethylliner liner of having put is put into the ultrasonic 10min of ultrasonic apparatus, proceed in stainless steel still, sealing.
(3) the stainless steel still of good seal is put into baking oven, carries out hydro-thermal reaction, is warmed up to 120 ℃ in half an hour, is incubated 24 hours.Naturally cool to room temperature, after hydro-thermal, as shown in Figure 7, XRD figure picture as shown in Figure 9 for the SEM photo of gained sample.
(4) with glue head dropper, reaction product is sucked in centrifuge tube, with the speed centrifugation of 1500-2000 rev/min, the time is 5 minutes.Gained precipitate with deionized water and dehydrated alcohol difference centrifuge washing 3 times, dry in 80 ℃ of baking ovens.Obtain required sample.
Embodiment 7
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately weigh cyclopentadienyl titanium dichloride 20mg, put into the polytetrafluoroethylliner liner of 20ml capacity.Add deionized water 10ml, 2 of quadrols, controlling pH value is 9.
(2) the above-mentioned mixed solution polytetrafluoroethylliner liner of having put is put into the ultrasonic 10min of ultrasonic apparatus, proceed in stainless steel still, sealing.
(3) the stainless steel still of good seal is put into baking oven, carries out hydro-thermal reaction, is warmed up to 120 ℃ in half an hour, is incubated 48 hours.Naturally cool to room temperature, after hydro-thermal, as shown in Figure 8, XRD figure picture as shown in Figure 9 for the SEM photo of gained sample.
(4) with glue head dropper, reaction product is sucked in centrifuge tube, with the speed centrifugation of 1500-2000 rev/min, the time is 5 minutes.Gained precipitate with deionized water and dehydrated alcohol difference centrifuge washing 3 times, dry in 80 ℃ of baking ovens.Obtain required sample.
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately take cyclopentadienyl titanium dichloride and be dissolved in deionized water, controlled concentration is 2mg/ml, drips wherein quadrol under stirring, and the pH value of controlling solution is 9, by solution through ultrasonic oscillation 10min;
(2) above-mentioned solution is proceeded in polytetrafluoro hydrothermal reaction kettle inner bag, with stainless steel outer sleeve encapsulation, be placed in baking oven, controlling temperature is 120 ℃ of insulation 24h;
(3) above-mentioned hydro-thermal reaction naturally cools to room temperature after finishing, and then with deionized water, dehydrated alcohol, distinguishes centrifuge washing sample 3 times, and the rotating speed of whizzer is 1500rpm, and gained sample is through oven for drying;
(4) sample of oven dry is put into porcelain boat, controlling temperature rise rate is 5 ℃/min, is warmed up to 400 ℃ in tube furnace, and insulation reaction 2h, obtains product.
In described centrifuge washing.
Embodiment 9
Utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, comprise the following steps:
(1) accurately take cyclopentadienyl titanium dichloride and be dissolved in deionized water, controlled concentration is 2mg/ml, drips wherein quadrol under stirring, and the pH value of controlling solution is 9, by solution through ultrasonic oscillation 15min;
(2) above-mentioned solution is proceeded in polytetrafluoro hydrothermal reaction kettle inner bag, with stainless steel outer sleeve encapsulation, be placed in baking oven, controlling temperature is 160 ℃ of insulation 1h;
(3) above-mentioned hydro-thermal reaction naturally cools to room temperature after finishing, and then with deionized water, dehydrated alcohol, distinguishes centrifuge washing sample 3 times, and the rotating speed of whizzer is 3000rpm, and gained sample is through oven for drying;
(4) sample of oven dry is put into porcelain boat, controlling temperature rise rate is 10 ℃/min, is warmed up to 500 ℃ in tube furnace, and insulation reaction 2h, obtains product.
Claims (2)
1. utilize cyclopentadienyl titanium dichloride cracking for a method for titanium dioxide nano-sphere, it is characterized in that, the method comprises the following steps:
(1) accurately take cyclopentadienyl titanium dichloride and be dissolved in deionized water, controlled concentration is 2mg/ml, drips wherein quadrol under stirring, and the pH value of controlling solution is 9, by solution through ultrasonic oscillation 10-15min;
(2) above-mentioned solution is proceeded in polytetrafluoro hydrothermal reaction kettle inner bag, with stainless steel outer sleeve encapsulation, be placed in baking oven, controlling temperature is 120-160 ℃ of insulation 1-24h;
(3) above-mentioned hydro-thermal reaction naturally cools to room temperature after finishing, and then with deionized water, dehydrated alcohol, distinguishes centrifuge washing sample 3 times, and gained sample is through oven for drying;
(4) sample of oven dry is put into porcelain boat, controlling temperature rise rate is 5-10 ℃/min, is warmed up to 400-500 ℃ in tube furnace, and insulation reaction 2h, obtains product.
2. a kind of cyclopentadienyl titanium dichloride cracking that utilizes according to claim 1, for the method for titanium dioxide nano-sphere, is characterized in that, in described centrifuge washing, the rotating speed of whizzer is 1500-3000rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110048647.8A CN102653416B (en) | 2011-03-01 | 2011-03-01 | Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110048647.8A CN102653416B (en) | 2011-03-01 | 2011-03-01 | Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102653416A CN102653416A (en) | 2012-09-05 |
| CN102653416B true CN102653416B (en) | 2014-01-29 |
Family
ID=46729167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110048647.8A Expired - Fee Related CN102653416B (en) | 2011-03-01 | 2011-03-01 | Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102653416B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618022B (en) * | 2016-01-12 | 2018-09-18 | 遵义医学院 | A kind of mesoporous hydrous titanium oxide raw powder's production technology of high activity |
| CN117752558B (en) * | 2023-12-22 | 2024-06-07 | 广州亿彩生物科技有限公司 | Moisturizing anti-inflammatory magnetic lip balm and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6517804B1 (en) * | 2000-02-29 | 2003-02-11 | Korea Atomic Energy Institute | TiO2 ultrafine powder, and process for preparing thereof |
| CN1418820A (en) * | 2002-12-18 | 2003-05-21 | 武汉大学 | Nano Titanium dioxide, prepn. process and use thereof |
| CN101306800A (en) * | 2008-07-04 | 2008-11-19 | 中国科学院化学研究所 | Method for preparing metallic oxide nano granules |
| CN101462042A (en) * | 2009-01-14 | 2009-06-24 | 华中师范大学 | Controllable one-pan method for preparing high-efficient titanic oxide mixed crystal photocatalyst |
-
2011
- 2011-03-01 CN CN201110048647.8A patent/CN102653416B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6517804B1 (en) * | 2000-02-29 | 2003-02-11 | Korea Atomic Energy Institute | TiO2 ultrafine powder, and process for preparing thereof |
| CN1418820A (en) * | 2002-12-18 | 2003-05-21 | 武汉大学 | Nano Titanium dioxide, prepn. process and use thereof |
| CN101306800A (en) * | 2008-07-04 | 2008-11-19 | 中国科学院化学研究所 | Method for preparing metallic oxide nano granules |
| CN101462042A (en) * | 2009-01-14 | 2009-06-24 | 华中师范大学 | Controllable one-pan method for preparing high-efficient titanic oxide mixed crystal photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102653416A (en) | 2012-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Boonprakob et al. | Enhanced visible-light photocatalytic activity of g-C3N4/TiO2 films | |
| CN106914263B (en) | Preparation method of composite visible light catalyst | |
| CN101890344B (en) | Preparation method of graphene/titanium dioxide composite photocatalyst | |
| Gu et al. | A novel incorporating style of polyaniline/TiO2 composites as effective visible photocatalysts | |
| Ramimoghadam et al. | Biotemplated synthesis of anatase titanium dioxide nanoparticles via lignocellulosic waste material | |
| CN104998672B (en) | A kind of g C3N4/{001}TiO2Composite visible light catalyst and preparation method and application | |
| CN105964236A (en) | Preparing method for graphene/titanium dioxide photocatalyst | |
| CN103641163B (en) | Preparation method of nano TiO2 powder and method for preparing oxygen gas indicator from nano TiO2 powder | |
| Gholami et al. | Photocatalytic degradation of methylene blue on TiO 2@ SiO 2 core/shell nanoparticles: Synthesis and characterization | |
| Li et al. | Ultrasonic aerosol spray-assisted preparation of TiO2/In2O3 composite for visible-light-driven photocatalysis | |
| CN108855220B (en) | Titanium dioxide doped ZIF and preparation method and application thereof | |
| CN102335602A (en) | Bismuth tungstate composite photocatalyst, preparation method thereof, and application thereof | |
| CN112007632B (en) | Flower-shaped SnO 2 /g-C 3 N 4 Preparation method of heterojunction photocatalyst | |
| Hang et al. | Influence of annealing temperature on physical properties and photocatalytic ability of g-C3N4 nanosheets synthesized through urea polymerization in Ar atmosphere | |
| CN105903486A (en) | Z-type photocatalyst and preparation method thereof | |
| CN105217676B (en) | Titania aerogel with nanometer sheet and nano-porous structure and preparation method thereof | |
| CN103657623A (en) | Microballoon-type titanium dioxide photocatalyst and preparation method thereof | |
| Nandanwar et al. | Preparation of TiO2/SiO2 nanocomposite with non-ionic surfactants via sol-gel process and their photocatalytic study | |
| CN107522169A (en) | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide | |
| Cao et al. | Co-electrospinning fabrication and photocatalytic performance of TiO2/SiO2 core/sheath nanofibers with tunable sheath thickness | |
| CN102653416B (en) | Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking | |
| CN106311100B (en) | A kind of production method of photocatalysis complex microsphere | |
| CN106111107B (en) | A kind of Zinc oxide nano sheet catalyst of titania additive | |
| Kumar et al. | Hydrothermal synthesis of anatase titanium dioxide mesoporous microspheres and their antimicrobial activity | |
| CN106975484A (en) | The preparation method and applications of ordered mesoporous titanium dioxide nanogold composite 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140129 Termination date: 20170301 |