CN102139915B - Method for preparing calcium titanate nanospheres - Google Patents
Method for preparing calcium titanate nanospheres Download PDFInfo
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- CN102139915B CN102139915B CN 201110099171 CN201110099171A CN102139915B CN 102139915 B CN102139915 B CN 102139915B CN 201110099171 CN201110099171 CN 201110099171 CN 201110099171 A CN201110099171 A CN 201110099171A CN 102139915 B CN102139915 B CN 102139915B
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Abstract
The invention relates to a method for preparing calcium titanate nanospheres. The method comprises the following steps of: adding a mineralizing agent, namely potassium hydroxide, into hydrothermal reaction materials, namely titanium hydroxide coprecipitate and deionized water solution of calcium nitrate; introducing solution obtained by hydrothermally decomposing glucose into a hydrothermal system to influence nucleation and control the shapes of products; and synthesizing the calcium titanate nanospheres of which the diameter is 200 to 1,000nm by hydrothermal reaction. The calcium titanate nanospheres are synthesized for the first time; the process is simple and is easy to control; the method is environment-friendly and low in cost; and the products are easy to produce.
Description
Technical field
The present invention relates to a kind of preparation method of calcium titanate nanospheres, belong to field of inorganic nonmetallic material.
Background technology
The oxide compound of perovskite structure becomes the focus of functional oxide investigation of materials because of its abundant physical properties.Perovskite oxide functional materials excellent performance, so broad research, development of practical is worth, and promotes continuous renewal and the progress of modern material industry.
The main energy sources of using in the world at present is the fossil class A fuel A, it is shortage of resources not only, the problem of environmental pollution that brings in its consumption process is also day by day outstanding. and by means of semiconductor catalyst, water of decomposition produces clean energy hydrogen under solar light irradiation, become the research direction of very attractive, the calcium titanate photocatalysis performance is widely studied.
Calcium titanate never stopped the research to it as being the perovskite structure of finding the earliest.Because its abundant raw material is with low cost, and it has higher specific inductivity and negative temperature coefficient, can develop multiple application device.At present, at home and abroad the calcium titanate pottery has been made the radio ceramics electrical condenser of miniaturized high capacity by extensive conduct, such as coupling, bypass, energy storage, and the material of partition direct current capacitors etc.
Summary of the invention
The object of the present invention is to provide the preparation method of the simple calcium titanate nanospheres of a kind of technique.
The preparation method of calcium titanate nanospheres of the present invention may further comprise the steps:
1) tetrabutyl titanate is dissolved in ethylene glycol monomethyl ether, the Ti in the regulator solution
4+Ionic concn is 0.5～1.0mol/L;
2) under whipped state, to 1) add the ammonia soln of the mass concentration 30% of 1 ~ 2ml in the tetrabutyl titanate ethylene glycol monomethyl ether solution that makes, precipitation, filtration, washed with de-ionized water obtain the co-precipitation of titanium oxyhydroxide;
3) nitrocalcite is dissolved in deionized water, forms calcium nitrate aqueous solution, Ca in the regulator solution
2+Concentration is 1.5～3.0mol/L;
4) potassium hydroxide is dissolved in deionized water, configuration concentration is the potassium hydroxide aqueous solution of 2 ~ 5mol/L;
5) with the co-precipitation of titanium oxyhydroxide, calcium nitrate aqueous solution, glucose and potassium hydroxide particle or potassium hydroxide aqueous solution join in the reactor inner bag, mixed aqueous solution with reaction mass in the deionized water conditioned reaction still inner bag reaches 70% ~ 90% of reactor volume, stirred at least 10 minutes, in the reaction mass mixed aqueous solution, the molecular volume mark of the oxyhydroxide of titanium is 0.1～0.2mol/L, wherein the molar ratio of calcium and titanium is 2 ~ 4, the molecular volume mark of potassium hydroxide is 0.5～1.5mol/L, and the molecular volume mark of glucose is 0.05 ~ 0.3mol/L; The volume radix of molecular volume mark is the volume of material in all reactor inner bags;
The reactor inner bag that 6) will dispose reaction mass is enclosed within the reactor, and sealing is 160
oC～240
oThen C insulation reaction 4～24 hours, cools to room temperature, takes out reaction product, filters, and uses successively dilute nitric acid solution and the washed with de-ionized water of deionized water, 0.5wt%, 60
oC～80
oThe C oven dry is 400 ~ 600
oC annealing 1 ~ 3h obtains calcium titanate nanospheres.
Step 4 of the present invention) in, potassium hydroxide can be that potassium hydroxide is dissolved in the deionized water, joins in the reactor with the form of solution, perhaps also can Granular forms join in the reactor.
Among the present invention, the reactor that uses is polytetrafluoroethylliner liner, the reactor that the stainless steel external member is airtight.
Among the present invention, used tetrabutyl titanate, nitrocalcite, potassium hydroxide, glucose and ammoniacal liquor and ethylene glycol monomethyl ether purity all are not less than chemical pure.
The present invention introduces the G/W thermolysis in hydrothermal system affect forming core, utilizes the hydro-thermal reaction method directly to prepare calcium titanate nanospheres, and its diameter is at 200nm～1000nm.Technological process of the present invention simply is easy to control, and is pollution-free, cost is low, is easy to produce.Calcium titanate of the present invention has very wide prospect at microelectronic device, catalyzer, solar cell, luminescent material, dielectric materials etc.
Description of drawings
Calcium titanate nanospheres scanning electron microscope (SEM) photo that Fig. 1 the present invention synthesizes.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Example 1
1) tetrabutyl titanate is dissolved in ethylene glycol monomethyl ether, the Ti in the regulator solution
4+Ionic concn is 0.5mol/L;
2) under whipped state, to 1) add the ammonia soln of the mass concentration 30% of 1.5ml in the tetrabutyl titanate ethylene glycol monomethyl ether solution that makes, precipitation, filtration, washed with de-ionized water 6 times obtain the co-precipitation of titanium oxyhydroxide;
3) nitrocalcite is dissolved in deionized water, Ca in the regulator solution
2+Ionic concn is 1.5mol/L;
4) potassium hydroxide is dissolved in deionized water, configuration concentration is the potassium hydroxide aqueous solution of 2mol/L;
5) co-precipitation of titanium oxyhydroxide, calcium nitrate aqueous solution, glucose and potassium hydroxide aqueous solution are joined in the reactor inner bag, mixed aqueous solution with reaction mass in the deionized water conditioned reaction still inner bag reaches 90% of reactor volume, stirred at least 10 minutes, in the reaction mass mixed aqueous solution, the molecular volume mark of the oxyhydroxide of titanium is 0.1mol/L, wherein the molar ratio of calcium and titanium is 3, the molecular volume mark of potassium hydroxide is 0.5mol/L, and the molecular volume mark of glucose is 0.1mol/L; The volume radix of molecular volume mark is the volume of material in all reactor inner bags;
6) the reactor inner bag that step 5) is disposed reaction mass is enclosed within the reactor, and sealing is 200
oThen C insulation reaction 12 hours, cools to room temperature, takes out reaction product, filters, and uses successively dilute nitric acid solution and the washed with de-ionized water of deionized water, 0.5wt%, 80
oThe C oven dry is 450
oThe C 2h that anneals obtains calcium titanate nanospheres.Its scanning electron microscope (SEM) photo as shown in Figure 1.
Example 2
1) tetrabutyl titanate is dissolved in ethylene glycol monomethyl ether, the Ti in the regulator solution
4+Ionic concn is 1.0mol/L;
2) under whipped state, to 1) add the ammonia soln of the mass concentration 30% of 1.5ml in the tetrabutyl titanate ethylene glycol monomethyl ether solution that makes, precipitation, filtration, washed with de-ionized water 6 times obtain the co-precipitation of titanium oxyhydroxide;
3) nitrocalcite is dissolved in deionized water, Ca in the regulator solution
2+Ionic concn is 2mol/L;
4) potassium hydroxide is dissolved in deionized water, configuration concentration is the potassium hydroxide aqueous solution of 2mol/L;
5) co-precipitation of titanium oxyhydroxide, calcium nitrate aqueous solution, glucose and potassium hydroxide aqueous solution are joined in the reactor inner bag, mixed aqueous solution with reaction mass in the deionized water conditioned reaction still inner bag reaches 90% of reactor volume, stirred at least 10 minutes, in the reaction mass mixed aqueous solution, the molecular volume mark of the oxyhydroxide of titanium is 0.2mol/L, wherein the molar ratio of calcium and titanium is 2, the molecular volume mark of potassium hydroxide is 0.5mol/L, and the molecular volume mark of glucose is 0.1mol/L; The volume radix of molecular volume mark is the volume of material in all reactor inner bags;
6) the reactor inner bag that step 5) is disposed reaction mass is enclosed within the reactor, and sealing is 200
oThen C insulation reaction 12 hours, cools to room temperature, takes out reaction product, filters, and uses successively dilute nitric acid solution and the washed with de-ionized water of deionized water, 0.5wt%, 60
oThe C oven dry is 500
oThe C 2h that anneals obtains calcium titanate nanospheres.The calcium titanate nanospheres diameter is at 200nm ~ 1000nm.
Example 3
1) tetrabutyl titanate is dissolved in ethylene glycol monomethyl ether, the Ti in the regulator solution
4Ionic concn is 0.6 mol/L;
2) under whipped state, to 1) add the ammonia soln of the mass concentration 30% of 1.0ml in the tetrabutyl titanate ethylene glycol monomethyl ether solution that makes, precipitation, filtration, washed with de-ionized water 6 times obtain the co-precipitation of titanium oxyhydroxide;
3) nitrocalcite is dissolved in deionized water, Ca in the regulator solution
2+Ionic concn is 2.4mol/L;
4) potassium hydroxide is dissolved in deionized water, configuration concentration is the potassium hydroxide aqueous solution of 2mol/L;
5) co-precipitation of titanium oxyhydroxide, calcium nitrate aqueous solution, glucose and potassium hydroxide aqueous solution are joined in the reactor inner bag, mixed aqueous solution with reaction mass in the deionized water conditioned reaction still inner bag reaches 90% of reactor volume, stirred at least 10 minutes, in the reaction mass mixed aqueous solution, the molecular volume mark of the oxyhydroxide of titanium is 0.12mol/L, wherein the molar ratio of calcium, titanium is 3, the molecular volume mark of potassium hydroxide is 0.5mol/L, and the molecular volume mark of glucose is 0.2mol/L; The volume radix of molecular volume mark is the volume of material in all reactor inner bags;
6) the reactor inner bag that step 5) is disposed reaction mass is enclosed within the reactor, and sealing is 200
oThen C insulation reaction 12 hours, cools to room temperature, takes out reaction product, filters, and uses successively dilute nitric acid solution and the washed with de-ionized water of deionized water, 0.5wt%, 80
oThe C oven dry is 600
oThe C 1h that anneals obtains calcium titanate nanospheres.The calcium titanate nanospheres diameter is at 200nm ~ 1000nm.
Claims (3)
1. the preparation method of a calcium titanate nanospheres is characterized in that may further comprise the steps:
1) tetrabutyl titanate is dissolved in ethylene glycol monomethyl ether, the Ti in the regulator solution
4+Ionic concn is 0.5～1.0mol/L;
2) under whipped state, to 1) add the ammonia soln of the mass concentration 30% of 1 ~ 2mL in the tetrabutyl titanate ethylene glycol monomethyl ether solution that makes, precipitation, filtration, washed with de-ionized water obtain the co-precipitation of titanium oxyhydroxide;
3) nitrocalcite is dissolved in deionized water, forms calcium nitrate aqueous solution, Ca in the regulator solution
2+Concentration is 1.5～3.0mol/L;
4) potassium hydroxide is dissolved in deionized water, compound concentration is the potassium hydroxide aqueous solution of 2 ~ 5mol/L;
5) with the co-precipitation of titanium oxyhydroxide, calcium nitrate aqueous solution, glucose and potassium hydroxide particle or potassium hydroxide aqueous solution join in the reactor inner bag, mixed aqueous solution with reaction mass in the deionized water conditioned reaction still inner bag reaches 70% ~ 90% of reactor volume, stirred at least 10 minutes, in the reaction mass mixed aqueous solution, the molecular volume mark of titanium oxyhydroxide is 0.1～0.2mol/L, wherein the molar ratio of calcium and titanium is 2 ~ 4, the molecular volume mark of potassium hydroxide is 0.5～1.5mol/L, and the molecular volume mark of glucose is 0.05 ~ 0.3mol/L; The volume radix of molecular volume mark is the volume of material in all reactor inner bags;
6) preparation the is responded reactor inner bag of material is enclosed within the reactor, and sealing is 160
oC～240
oThen C insulation reaction 4～24 hours, cools to room temperature, takes out reaction product, filters, and uses successively dilute nitric acid solution and the washed with de-ionized water of deionized water, 0.5wt%, 60
oC～80
oThe C oven dry is 400 ~ 600
oC annealing 1 ~ 3h obtains calcium titanate nanospheres, and the diameter of nanometer ball is at 200nm～1000nm.
2. the preparation method of calcium titanate nanospheres according to claim 1 is characterized in that reactor is polytetrafluoroethylliner liner, the reactor that the stainless steel external member is airtight.
3. the preparation method of calcium titanate nanospheres according to claim 1 is characterized in that used tetrabutyl titanate, nitrocalcite, potassium hydroxide, glucose and ammoniacal liquor and ethylene glycol monomethyl ether purity all are not less than chemical pure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102502797A (en) * | 2011-10-08 | 2012-06-20 | 哈尔滨工程大学 | Method for preparing calcium titanate with eggshells as raw material |
| CN102512708A (en) * | 2012-01-04 | 2012-06-27 | 中南大学 | Medical calcium titanate biological coating and preparation method thereof |
| CN102583514A (en) * | 2012-01-04 | 2012-07-18 | 中南大学 | Nano linear calcium titanate and synthesis method thereof |
| CN106040214B (en) * | 2016-05-31 | 2018-09-11 | 浙江大学 | A kind of preparation method of high activity calcium titanate/calcium hydroxide mixing photochemical catalyst |
| CN107487782A (en) * | 2017-09-29 | 2017-12-19 | 兰州理工大学 | A kind of CaTiO3The preparation method of nanometer pane |
| CN108448073B (en) * | 2018-02-01 | 2020-10-09 | 山东理工大学 | Lithium ion battery C @ TiO2Composite negative electrode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064431A (en) * | 1991-12-31 | 1992-09-16 | 巩义市金红石总厂 | Electric-melten calcium titanate product and manufacture method thereof |
| US20080261098A1 (en) * | 2007-04-20 | 2008-10-23 | General Electric Company | Proton-conducting membranes for electrochemical devices, and related articles and processes |
| CN101376523A (en) * | 2008-09-24 | 2009-03-04 | 东华大学 | Preparation of doped calcium titanate (CaTiO3: Eu3+) fluorescent powder |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064431A (en) * | 1991-12-31 | 1992-09-16 | 巩义市金红石总厂 | Electric-melten calcium titanate product and manufacture method thereof |
| US20080261098A1 (en) * | 2007-04-20 | 2008-10-23 | General Electric Company | Proton-conducting membranes for electrochemical devices, and related articles and processes |
| CN101376523A (en) * | 2008-09-24 | 2009-03-04 | 东华大学 | Preparation of doped calcium titanate (CaTiO3: Eu3+) fluorescent powder |
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