CN103073055A - Process for preparing titanium dioxide with network structure by using biological template method - Google Patents
Process for preparing titanium dioxide with network structure by using biological template method Download PDFInfo
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- CN103073055A CN103073055A CN2011103275869A CN201110327586A CN103073055A CN 103073055 A CN103073055 A CN 103073055A CN 2011103275869 A CN2011103275869 A CN 2011103275869A CN 201110327586 A CN201110327586 A CN 201110327586A CN 103073055 A CN103073055 A CN 103073055A
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Abstract
The invention brings forward a process for preparing titanium dioxide with a network structure by using a biological template method. The process is characterized by comprising the following steps: cleaning an egg shell and soaking the egg shell in a diluted hydrochloric acid solution to remove a calcium carbonate shell so as to obtain the biological template, i.e., an egg membrane; preparing a butyl titanate ethanol solution; drying the cleaned egg membrane in the air and soaking the egg membrane in the butyl titanate ethanol solution for a certain period of time; and taking the cleaned egg membrane out for natural air drying and calcining the cleaned egg membrane in a muffle furnace for a certain period of time so as to obtain titanium dioxide with the network structure. The process provided by the invention can be used for preparation of oxides of different kinds, presents versatility and has the advantages of simple process and flow, a wide adjustable scope of parameters, low cost, good repeatability, easily controllable conditions, suitability for mass synthesis, etc.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide, particularly relate to and a kind ofly syntheticly take eggshell membrane as biological template have a method of three-dimensional net structure titanium dioxide.The invention belongs to the synthesis technical field of micro/nano material.
Background technology
Titanium dioxide has stable chemical nature, nontoxic, indissoluble, the characteristic such as cheap, and titanium dioxide also is a kind of comparatively desirable semiconductor light-catalyst in addition, and the aspects such as pollutent in the large G﹠W of photocatalytic degradation have broad application prospects.
Nano titanium oxide also has the not available character of block titanium dioxide such as small-size effect, quantum size effect, specific surface area be large.The method for preparing nano titanium oxide mainly contains sol-gel method, chemical Vapor deposition process, alumina formwork method, anonizing and hydrothermal method etc.Because structure, the pattern of material can give material some special character, therefore in recent years, the investigator was devoted to synthetic TiO with specific morphology
2Nano material such as nanotube, nanometer rod, nano wire, nanometer ball etc., especially has than bigger serface, length-to-diameter ratio nano wire large, orientable conduction electron and receives much concern.And the nano-TiO of three-dimensional net structure
2Not only can simultaneously, can also increase the contact site for light induced electron provides fast transmission path, therefore, have the TiO of three-dimensional net structure
2Research significant.
Summary of the invention
The object of the invention is to adopt the get everything ready TiO of network structure of a kind of technique is simple, with low cost, condition is easily controlled, environmentally safe can be used for scale operation biological template legal system
2Method.
The present invention proposes the method for the standby network structure titanium dioxide of a kind of biological template legal system, and its feature comprises following processing step:
(1) preparation of biological template: Ovum crusta Gallus domesticus is cleaned, the film of outside is carefully peeled off, shell is put into acid solution, removes the calcium carbonate shell, and the inner layer film Automatic-falling takes out, and cleans, and soaks with physiological saline, and is stand-by;
(2) configuration butyl (tetra) titanate-ethanolic soln;
(3) distilled water flushing is used in the eggshell membrane taking-up of preparation in the step (1), after drying, be soaked in the solution of step (2) preparation, soak, take out, naturally dry;
(4) eggshell membrane that step (3) is dried is put into the retort furnace sintering, be warming up to certain temperature with certain temperature rise rate after, the constant temperature certain hour is cooled to room temperature and gets final product.
Acid solution described in the step (1) is a kind of or its combination in hydrochloric acid, the acetic acid.
The concentration of acid solution is 0.1mol/L～0.5mol/L described in the step (1).
The volume ratio of the butyl (tetra) titanate ethanolic soln described in the step (2) is 1:1～1:3.
Soak time described in the step (3) is 4～12 hours.
Sintering temperature described in the step (4) is 550 ℃～700 ℃.
Temperature rise rate described in the step (4) is 2 ℃/min～5 ℃/min.
Constant temperature time described in the step (4) is 2～4 hours.
The structure of the inventive method products therefrom, pattern, composition characterize, and select respectively X-ray powder diffraction (XRD), scanning electronic microscope (SEM), N
2The means such as adsorption specific surface area tester (BET) characterize.
The present invention can be used for preparing different types of oxide compound, has versatility; And the method has technique and simple flow, and the parameter variable range is wide, and is with low cost, and is repeatable strong, and condition is easily controlled, and the advantage such as can synthesize in a large number.
The invention has the advantages that:
1. biological template that the present invention adopts---eggshell membrane, material be easy to get, environmentally friendly.The complex structure of eggshell membrane, available its prepared little, the nano material of various novelties, even can make up extremely complicated nano-superstructure.
2. biological template converted in-situ legal system of the present invention is for the oxide compound of three-dimensional net structure, and synthetic method is simple, and whole preparation process is easy, and condition is easily controlled, and the convenient post-treatment of product, has very strong versatility.
3. preparation process of the present invention need not to use any special additive and catalyzer etc., so the present invention has economy, characteristics with low cost.
4. the present invention does not produce the by product that environment is had pollution in the preparation, meets the Sustainable development requirement, is a kind of environment-friendly type synthesis technique.Product pattern, the size of preparation are easily controlled, and purity is high, and better crystallinity degree and product are processed convenient succinct, are suitable for medium-scale industrial production.
Description of drawings
Fig. 1 is the XRD figure of the product of gained among the embodiment 1.
Fig. 2 is the SEM figure of the product of gained among the embodiment 1.
Fig. 3 is the SEM figure of the product of gained among the embodiment 2.
Fig. 4 is the SEM figure of the product of gained among the embodiment 4.
Embodiment
Further describe the present invention below by specific embodiment.
Embodiment 1:
A kind of synthesizing take eggshell membrane as biological template has three-dimensional net structure TiO
2Method, the method may further comprise the steps:
(1) hydrochloric acid soln of configuration 0.1M, butyl (tetra) titanate ethanolic soln (V:V=1:1);
(2) preparation of egg inner layer film: Ovum crusta Gallus domesticus is cleaned, the film of outside is all taken off, shell is put into the hydrochloric acid soln that diluted, and after the dissolving of calcium shell, the inner layer film Automatic-falling takes out, and cleans, and soaks with physiological saline, and is stand-by;
(3) the egg film in the step (2) is taken out, use distilled water flushing, after naturally drying, be immersed in 4h in the butyl (tetra) titanate ethanolic soln;
The egg film that (4) will be immersed in the butyl (tetra) titanate ethanolic soln takes out, and after naturally drying, puts into retort furnace and calcines.Condition is: the speed with 2 ℃/min is warming up to 100 ℃, insulation 0.5h, and then the speed with 2 ℃/min is warming up to 550 ℃, insulation 2h.
Products therefrom in the step (4) is characterized its structure and crystal formation with SEM, XRD, BET respectively, and Fig. 1,2,3 is the TiO of reaction conditions gained for this reason
2The pattern of three-dimensional net structure, crystalline form and specific surface area.As can be seen from the figure, the product of preparation has three-dimensional net structure, is the anatase octahedrite crystalline form from the crystal formation of the visible products obtained therefrom of X-ray powder diffraction collection of illustrative plates, and does not have other impurity peaks in the diffraction peak of XRD, shows that the degree of crystallinity of products therefrom is fine.The specific surface area of product is 52m
2/ g.This is network structure TiO
2Application lay a good foundation.
Embodiment 2:
A kind of synthesizing take eggshell membrane as biological template has three-dimensional net structure TiO
2Method, the method may further comprise the steps:
(1) hydrochloric acid soln of configuration 0.1M, butyl (tetra) titanate ethanolic soln (V:V=1:2);
(2) preparation of egg inner layer film: Ovum crusta Gallus domesticus is cleaned, the film of outside is all taken off, shell is put into the hydrochloric acid soln that diluted, and after the dissolving of calcium shell, the inner layer film Automatic-falling takes out, and cleans, and soaks with physiological saline, and is stand-by;
(3) the egg film in the step (2) is taken out, use distilled water flushing, after naturally drying, be immersed in 4h in the butyl (tetra) titanate ethanolic soln;
The egg film that (4) will be immersed in the butyl (tetra) titanate ethanolic soln takes out, and after naturally drying, puts into retort furnace and calcines.Condition is: the speed with 2 ℃/min is warming up to 100 ℃, insulation 0.5h, and then the speed with 2 ℃/min is warming up to 600 ℃, insulation 2h.
Products therefrom in the step (4) is characterized with SEM, as shown in Figure 3, as can be seen from the figure, the TiO for preparing with this understanding
2Still kept preferably network structure.
Embodiment 3:
A kind of synthesizing take eggshell membrane as biological template has three-dimensional net structure TiO
2Method, the method may further comprise the steps:
(1) hydrochloric acid soln of configuration 0.1M, butyl (tetra) titanate ethanolic soln (V:V=2:1);
(2) preparation of egg inner layer film: Ovum crusta Gallus domesticus is cleaned, the film of outside is all taken off, shell is put into the hydrochloric acid soln that diluted, and after the dissolving of calcium shell, the inner layer film Automatic-falling takes out, and cleans, and soaks with physiological saline, and is stand-by;
(3) the egg film in the step (2) is taken out, use distilled water flushing, after naturally drying, be immersed in 8h in the butyl (tetra) titanate ethanolic soln;
The egg film that (4) will be immersed in the butyl (tetra) titanate ethanolic soln takes out, and after naturally drying, puts into retort furnace and calcines.Condition is: the speed with 2 ℃/min is warming up to 100 ℃, insulation 0.5h, and then the speed with 2 ℃/min is warming up to 700 ℃, insulation 2h.
Embodiment 4:
A kind of synthesizing take eggshell membrane as biological template has three-dimensional net structure TiO
2Method, the method may further comprise the steps:
(1) hydrochloric acid soln of configuration 0.2M, butyl (tetra) titanate ethanolic soln (V:V=1:3);
(2) preparation of egg inner layer film: Ovum crusta Gallus domesticus is cleaned, the film of outside is all taken off, shell is put into the hydrochloric acid soln that diluted, and after the dissolving of calcium shell, the inner layer film Automatic-falling takes out, and cleans, and soaks with physiological saline, and is stand-by;
(3) the egg film in the step (2) is taken out, use distilled water flushing, after naturally drying, be immersed in 8h in the butyl (tetra) titanate ethanolic soln;
The egg film that (4) will be immersed in the butyl (tetra) titanate ethanolic soln takes out, and after naturally drying, puts into retort furnace and calcines.Condition is: the speed with 2 ℃/min is warming up to 100 ℃, insulation 0.5h, and then the speed with 5 ℃/min is warming up to 700 ℃, insulation 3h.
Products therefrom in the step (4) is characterized with SEM, as shown in Figure 4, as can be seen from the figure, the TiO for preparing with this understanding
2Network structure is destroyed, and this shows the too high pattern that can destroy product of temperature rise rate.
Embodiment 5:
A kind of synthesizing take eggshell membrane as biological template has three-dimensional net structure TiO
2Method, the method may further comprise the steps:
(1) hydrochloric acid soln of configuration 0.1M, butyl (tetra) titanate ethanolic soln (V:V=1:2);
(2) preparation of egg inner layer film: Ovum crusta Gallus domesticus is cleaned, the film of outside is all taken off, shell is put into the hydrochloric acid soln that diluted, and after the dissolving of calcium shell, the inner layer film Automatic-falling takes out, and cleans, and soaks with physiological saline, and is stand-by;
(3) the egg film in the step (2) is taken out, use distilled water flushing, after naturally drying, be immersed in 12h in the butyl (tetra) titanate ethanolic soln;
The egg film that is immersed in the butyl (tetra) titanate ethanolic soln is taken out, after naturally drying, put into retort furnace and calcine.Condition is: the speed with 2 ℃/min is warming up to 100 ℃, insulation 0.5h, and then the speed with 5 ℃/min is warming up to 700 ℃, insulation 4h.
Claims (8)
1. the method for the standby network structure titanium dioxide of a biological template legal system, its feature comprises following processing step:
(1) preparation of biological template: Ovum crusta Gallus domesticus is cleaned, the film of outside is carefully peeled off, shell is put into acid solution, removes the calcium carbonate shell, and the inner layer film Automatic-falling takes out, and cleans, and soaks with physiological saline, and is stand-by;
(2) configuration butyl (tetra) titanate-ethanolic soln;
(3) distilled water flushing is used in the eggshell membrane taking-up of preparation in the step (1), after drying, be soaked in the solution of step (2) preparation, soak, take out, naturally dry;
(4) eggshell membrane that step (3) is dried is put into the retort furnace sintering, be warming up to certain temperature with certain temperature rise rate after, the constant temperature certain hour is cooled to room temperature and gets final product.
2. described a kind of biological template legal system is characterized in that for the method for network structure titanium dioxide according to claim 1, and the acid solution described in the step (1) is a kind of or its combination in hydrochloric acid, the acetic acid.
3. described a kind of biological template legal system is characterized in that for the method for network structure titanium dioxide according to claim 1, and the concentration of acid solution is 0.1mol/L～0.5mol/L described in the step (1).
4. described a kind of biological template legal system is characterized in that for the method for network structure titanium dioxide according to claim 1, and the volume ratio of the butyl (tetra) titanate ethanolic soln described in the step (2) is 1:1～1:3.
5. described a kind of biological template legal system is characterized in that for the method for network structure titanium dioxide according to claim 1, and the soak time described in the step (3) is 4～12 hours.
6. described a kind of biological template legal system is characterized in that for the method for network structure titanium dioxide according to claim 1, and the sintering temperature described in the step (4) is 550 ℃～700 ℃.
7. the method for the standby network structure titanium dioxide of described a kind of biological template legal system according to claim 1 is characterized in that, the temperature rise rate described in the step (4) is 2 ℃/min～5 ℃/min.
8. described a kind of biological template legal system is characterized in that for the method for network structure titanium dioxide according to claim 1, and the constant temperature time described in the step (4) is 2～4 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288128A (en) * | 2013-06-25 | 2013-09-11 | 扬州大学 | A method for the synthesis of flaky anatase type titanium dioxide by using biological templates |
| CN105664947A (en) * | 2016-03-08 | 2016-06-15 | 济南大学 | Composite NiAl-LDH/gamma-AlO(OH)/C catalyst and preparation method thereof |
| CN108543529A (en) * | 2018-04-19 | 2018-09-18 | 华南农业大学 | A kind of preparation method for helping oxidative degradation additive with special appearance |
| CN109540866A (en) * | 2018-11-30 | 2019-03-29 | 泉州师范学院 | A kind of compound gold nano-material and preparation method thereof for Detecting Pesticide |
| CN110339836A (en) * | 2019-07-30 | 2019-10-18 | 泉州师范学院(石狮)生态智能织物工程技术研究院 | A kind of rodlike CuxO catalysis material and the preparation method and application thereof |
| CN112010349A (en) * | 2020-08-31 | 2020-12-01 | 广州钰芯传感科技有限公司 | Preparation method of chromium oxide nano material and application of chromium oxide nano material in gas-sensitive sensing |
-
2011
- 2011-10-25 CN CN2011103275869A patent/CN103073055A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| DONG YANG ET AL.: "Eggshell Membrane Templating of Hierarchically Ordered Macroporous Networks Composed of TiO2 Tubes", 《ADVANCED MATERIALS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288128A (en) * | 2013-06-25 | 2013-09-11 | 扬州大学 | A method for the synthesis of flaky anatase type titanium dioxide by using biological templates |
| CN105664947A (en) * | 2016-03-08 | 2016-06-15 | 济南大学 | Composite NiAl-LDH/gamma-AlO(OH)/C catalyst and preparation method thereof |
| CN108543529A (en) * | 2018-04-19 | 2018-09-18 | 华南农业大学 | A kind of preparation method for helping oxidative degradation additive with special appearance |
| CN108543529B (en) * | 2018-04-19 | 2021-05-04 | 华南农业大学 | Preparation method of oxidation-degradation-assisting additive with special morphology |
| CN109540866A (en) * | 2018-11-30 | 2019-03-29 | 泉州师范学院 | A kind of compound gold nano-material and preparation method thereof for Detecting Pesticide |
| CN110339836A (en) * | 2019-07-30 | 2019-10-18 | 泉州师范学院(石狮)生态智能织物工程技术研究院 | A kind of rodlike CuxO catalysis material and the preparation method and application thereof |
| CN110339836B (en) * | 2019-07-30 | 2022-03-15 | 泉州师范学院 | Rod-shaped CuxO photocatalytic material and preparation method and application thereof |
| CN112010349A (en) * | 2020-08-31 | 2020-12-01 | 广州钰芯传感科技有限公司 | Preparation method of chromium oxide nano material and application of chromium oxide nano material in gas-sensitive sensing |
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Application publication date: 20130501 |