CN1850622A - Method for preparing calcium molybdate self assembling body with hollow structure - Google Patents
Method for preparing calcium molybdate self assembling body with hollow structure Download PDFInfo
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- CN1850622A CN1850622A CN 200610026853 CN200610026853A CN1850622A CN 1850622 A CN1850622 A CN 1850622A CN 200610026853 CN200610026853 CN 200610026853 CN 200610026853 A CN200610026853 A CN 200610026853A CN 1850622 A CN1850622 A CN 1850622A
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Abstract
The invention relates to a method for preparing a calcium molybdate self-assembled body with hollow structure, adopting microemulsion as medium, firstly preparing equivalent calcium chloride water solution and sodium molybdate water solution with the same concentration with n-octane, n- butyl alcohol, and CTAB in a certain proportion into the respective transparent microemulsions, then mixing the two microemulsions, placing still and reacting at 8-25 deg.C, or reacting in hydrothermal kettle at 160 deg.C, so as to be able to make it. And it is directionally arranged of calcium molybdate grains, and its grain size can be controlled by reaction time or temperature, about 50-300 nm.
Description
Technical field
The present invention relates to a kind of preparation method with calcium molybdate self assembling body of hollow structure, adopting microemulsion is that media prepares the calcium molybdate particulate and aligns the hollow self-assembly that forms.Belong to the functional materials preparing technical field.
Background technology
The molybdate of scheelite-type structure, extremely people pay close attention to owing to have superior luminescent properties and good colour developing, discoloration effect.Molybdate can send the green glow or the orange light of single wavelength, and they might become the source of three primary colours in the color monitor, also might obtain to use in the jumbotron color monitor.In addition, molybdate can also be used to prepare aspects such as optical fiber, humidity sensor, luminescent material, magnetic material, catalytic material, anti-biotic material.
In recent years, along with the development of nanotechnology, the nano molybdate of preparation different-shape is studied its performance at aspects such as catalysis, magnetic, electrical, optical, becomes the research focus of countries in the world day by day.At present, the method for preparing nano molybdate mainly contains hard template method, soft template method, hydrothermal method, microemulsion method, the cooperation precipitator method etc.As: template prepares molybdate, needs to remove template after reaction finishes, and not only makes complicated operation, even can influence the product pattern; The Hydrothermal Preparation molybdate then needs the reaction conditions of High Temperature High Pressure, by contrast, that microemulsion method has is simple to operate, size is controlled, particle good dispersity, narrowly distributing, be easy to realize characteristics such as serialization production, and it is the variation route of preparation nanoparticle of growing up the eighties in 20th century.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, propose a kind of preparation method with calcium molybdate self assembling body of hollow structure,
For realizing this purpose, it is that media prepares calcium molybdate hollow self-assembly that the present invention adopts microemulsion, at first respectively calcium chloride water equivalent, same concentrations and sodium molybdate aqueous solution are mixed with transparent microemulsion with octane, propyl carbinol, cetyl trimethylammonium bromide (CTAB) by a certain percentage, then two kinds of microemulsions are mixed, 8～25 ℃ of following standing and reacting, perhaps 160 ℃ of reactions in water heating kettle can obtain to have the calcium molybdate self assembling body of hollow structure.Prepared calcium molybdate self assembling body is aligned by nanometer calcium molybdate particle and forms, and nano particle diameter can be by reaction times or temperature of reaction control, about 50～300nm.
Method of the present invention comprises following concrete steps:
1, the preparation of calcium ion microemulsion:
In Erlenmeyer flask, add a certain amount of octane, propyl carbinol, cetyl trimethylammonium bromide (CTAB) successively, add the solubility calcium salt brine solution of certain volume under the magnetic agitation.Stirred 30 minutes, and formed the calcium ion microemulsion of homogeneous phase transparent.Wherein the concentration of CTAB is 0.15～0.25moll
-1, the mol ratio of propyl carbinol and CTAB is 3.47～4.52, the mole number of water is 33 with the ratio of CTAB mole number in the solubility calcium salt brine solution, soluble calcium salt concentration of aqueous solution 0.1～0.8moll
-1
2, the preparation of molybdenum acid ion microemulsion:
According to step 1, substitute the solubility calcium salt brine solution with same concentrations, equal-volume sodium molybdate aqueous solution, obtain forming identical molybdenum acid ion microemulsion with the calcium ion microemulsion.
The said soluble calcium salt of the present invention is: Calcium Chloride Powder Anhydrous, nitrocalcite.
3, calcium molybdate self assembling body is synthetic:
Calcium ion microemulsion and molybdenum acid ion microemulsion with above-mentioned acquisition, under the magnetic agitation condition, mix rapidly, the mixed solution that obtains 8～25 ℃ of following standing and reacting, is perhaps moved into 160 ℃ of reactions in the tetrafluoroethylene water heating kettle that stainless steel casing is arranged, 1 minute～16 hours reaction times; Naturally cool to room temperature then, centrifugation is repeatedly washed with deionized water and dehydrated alcohol, and 60 ℃ of vacuum dryings 6 hours can obtain to have the calcium molybdate self assembling body of hollow structure.
Method temperature of reaction of the present invention is low, and the reaction times is short, the shortest need 1 minute, and operation steps is simple, and cost is low, productive rate height, favorable repeatability.It is media that the present invention has adopted microemulsion, makes the size of nanoparticle to be about 50～300nm by reaction times or temperature of reaction control, has avoided the rapid generation of initial reaction stage bulky crystal.The calcium molybdate self-assembled structures of preparation is dumbbell shaped, flower-shaped (hollow), starfish shape (hollow), is aligned by nanometer calcium molybdate particle to form, and particle diameter prolonged and increases with temperature of reaction rising, reaction times.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the embodiment of the invention 1 resulting dumbbell shaped calcium molybdate self assembling body.(embodiment 1-4 has identical x-ray diffraction pattern).
Fig. 2 is the field emission scanning electron microscope photo and the transmission electron microscope photo of the embodiment of the invention 1 resulting dumbbell shaped calcium molybdate self assembling body.
Fig. 3 is the field emission scanning electron microscope photo and the transmission electron microscope photo of the embodiment of the invention 2 resulting flower-shaped calcium molybdate self assembling bodies.
Fig. 4 is the field emission scanning electron microscope photo and the transmission electron microscope photo of the embodiment of the invention 3 resulting starfish shape calcium molybdate self assembling bodies.
Fig. 5 is the field emission scanning electron microscope photo of the embodiment of the invention 4 resulting flower-shaped calcium molybdate self assembling bodies.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
1) in a 50ml Erlenmeyer flask, adds 13.42ml octane, 1.08ml propyl carbinol, 1.2g cetyl trimethylammonium bromide (CTAB) successively, add the 0.5moll of 2ml under the magnetic agitation
-1Calcium chloride water.Stirred 30 minutes, and formed the calcium ion microemulsion of homogeneous phase transparent.
2) in a 50ml Erlenmeyer flask, add 13.42ml octane, 1.08ml propyl carbinol, 1.2g cetyl trimethylammonium bromide (CTAB) successively, add the 0.5moll of 2ml under the magnetic agitation
-1Sodium molybdate aqueous solution.Stirred 30 minutes, and formed the molybdenum acid ion microemulsion of homogeneous phase transparent.
3) with the above-mentioned two kinds microemulsions that contain calcium chloride and Sodium orthomolybdate respectively under the magnetic agitation condition, mix rapidly, 8 ℃ of following standing and reacting 1 hour.After reaction finished, centrifugation was repeatedly washed with deionized water and dehydrated alcohol, and 60 ℃ of vacuum dryings 6 hours can obtain the self-assembly of dumbbell shaped calcium molybdate particulate.
The x-ray diffraction pattern of resulting dumbbell shaped calcium molybdate self assembling body such as Fig. 1.Prepared as seen from Figure 1 material is the tetragonal structure calcium molybdate.Fig. 2 is field emission scanning electron microscope photo and the transmission electron microscope photo that obtains the dumbbell shaped calcium molybdate self assembling body.As seen from the figure, the about 3 μ m of this packaging assembly size are aligned by the particle of particle diameter 50～100nm and to form.
Embodiment 2
1) in a 50ml Erlenmeyer flask, adds 13.42ml octane, 1.08ml propyl carbinol, 1.2g cetyl trimethylammonium bromide (CTAB) successively, add the 0.5moll of 2ml under the magnetic agitation
-1Calcium chloride water.Stirred 30 minutes, and formed the calcium ion microemulsion of homogeneous phase transparent.
2) in a 50ml Erlenmeyer flask, add 13.42ml octane, 1.08ml propyl carbinol, 1.2g cetyl trimethylammonium bromide (CTAB) successively, add the 0.5moll of 2ml under the magnetic agitation
-1Sodium molybdate aqueous solution.Stirred 30 minutes, and formed the molybdenum acid ion microemulsion of homogeneous phase transparent.
3) with the above-mentioned two kinds microemulsions that contain calcium chloride and Sodium orthomolybdate respectively under the magnetic agitation condition, mix rapidly, 25 ℃ of following standing and reacting 1 minute.After reaction finished, centrifugation was repeatedly washed with deionized water and dehydrated alcohol, and 60 ℃ of vacuum dryings 6 hours can obtain the self-assembly of flower-shaped calcium molybdate particulate.
Fig. 3 is resulting flower-shaped calcium molybdate self assembling body field emission scanning electron microscope photo and transmission electron microscope photo.As seen from the figure, the about 2 μ m of this packaging assembly size are aligned by the particle of particle diameter 50～150nm and to form.
Embodiment 3
1) in a 50ml Erlenmeyer flask, adds 13.42ml octane, 1.08ml propyl carbinol, 1.2g cetyl trimethylammonium bromide (CTAB) successively, add the 0.2moll of 2ml under the magnetic agitation
-1Calcium nitrate aqueous solution.Stirred 30 minutes, and formed the calcium ion microemulsion of homogeneous phase transparent.
2) in a 50ml Erlenmeyer flask, add 13.42ml octane, 1.08ml propyl carbinol, 1.2g cetyl trimethylammonium bromide (CTAB) successively, add the 0.2moll of 2ml under the magnetic agitation
-1Sodium molybdate aqueous solution.Stirred 30 minutes, and formed the molybdenum acid ion microemulsion of homogeneous phase transparent.
3) with the above-mentioned two kinds microemulsions that contain nitrocalcite and Sodium orthomolybdate respectively under the magnetic agitation condition, equal-volume mixes rapidly, 25 ℃ of following standing and reacting 1 hour.After reaction finished, centrifugation was repeatedly washed with deionized water and dehydrated alcohol, and 60 ℃ of vacuum dryings 6 hours can obtain the self-assembly of starfish shape calcium molybdate particulate.
Fig. 4 is resulting starfish shape calcium molybdate self assembling body field emission scanning electron microscope photo and transmission electron microscope photo.As seen from the figure, the about 2 μ m of this packaging assembly size are aligned by the particle of particle diameter 50～150nm and to form.
Embodiment 4
1) in a 50ml Erlenmeyer flask, adds 13.42ml octane, 1.08ml propyl carbinol, 1.2g cetyl trimethylammonium bromide (CTAB) successively, add the 0.5moll of 2ml under the magnetic agitation
-1Calcium chloride water.Stirred 30 minutes, and formed the calcium ion microemulsion of homogeneous phase transparent.
2) in a 50ml Erlenmeyer flask, add 13.42ml octane, 1.08ml propyl carbinol, 1.2g cetyl trimethylammonium bromide (CTAB) successively, add the 0.5moll of 2ml under the magnetic agitation
-1Sodium molybdate aqueous solution.Stirred 30 minutes, and formed the molybdenum acid ion microemulsion of homogeneous phase transparent.
3) with the above-mentioned two kinds microemulsions that contain calcium chloride and Sodium orthomolybdate respectively under the magnetic agitation condition, equal-volume mixes rapidly, moves in the tetrafluoroethylene water heating kettle that stainless steel casing is arranged of 50ml, and is warming up to 160 ℃ of reactions 16 hours.After reaction finishes, naturally cool to room temperature, centrifugation is repeatedly washed with deionized water and dehydrated alcohol, and 60 ℃ of vacuum dryings 6 hours can obtain the self-assembly of flower-shaped calcium molybdate particulate.
Fig. 4 is resulting flower-shaped calcium molybdate self assembling body field emission scanning electron microscope photo.As seen from the figure, the about 2 μ m of this packaging assembly size are aligned by the particle of particle diameter 150～300nm and to form.
Claims (2)
1, a kind of preparation method with calcium molybdate self assembling body of hollow structure is characterized in that comprising the steps:
1) preparation of calcium ion microemulsion: in Erlenmeyer flask, add octane, propyl carbinol, cetyl trimethylammonium bromide successively, add the solubility calcium salt brine solution under the magnetic agitation, stirred 30 minutes, form the calcium ion microemulsion of homogeneous phase transparent; Wherein the concentration of cetyl trimethylammonium bromide is 0.15～0.25moll
-1, the mol ratio of propyl carbinol and cetyl trimethylammonium bromide is 3.47～4.52, the mole number of water is 33 with the ratio of cetyl trimethylammonium bromide mole number in the solubility calcium salt brine solution, soluble calcium salt concentration of aqueous solution 0.1～0.8moll
-1
2) preparation of molybdenum acid ion microemulsion: according to step 1), substitute the solubility calcium salt brine solution, obtain forming identical molybdenum acid ion microemulsion with the calcium ion microemulsion with same concentrations, equal-volume sodium molybdate aqueous solution;
3) calcium molybdate self assembling body is synthetic: the calcium ion microemulsion and the molybdenum acid ion microemulsion of above-mentioned acquisition are mixed rapidly under the magnetic agitation condition, with the mixed solution that obtains 8～25 ℃ of following standing and reacting, perhaps move into 160 ℃ of reactions in the tetrafluoroethylene water heating kettle that stainless steel casing is arranged, 1 minute～16 hours reaction times; Naturally cooling then, centrifugation, with deionized water and absolute ethanol washing, 60 ℃ of vacuum dryings 6 hours promptly obtain to have the calcium molybdate self assembling body of hollow structure.
2, according to the preparation method of the calcium molybdate self assembling body with hollow structure of claim 1, it is characterized in that described soluble calcium salt is Calcium Chloride Powder Anhydrous or nitrocalcite.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717120B (en) * | 2009-12-14 | 2011-08-03 | 上海应用技术学院 | Solvent thermal induction control synthesis method for nano molybdate with scheelite structure |
| CN105470489A (en) * | 2016-01-11 | 2016-04-06 | 福建师范大学泉港石化研究院 | Preparation method of MoO2 hollow microsphere material for high-performance lithium ion battery |
| CN107651713A (en) * | 2017-11-14 | 2018-02-02 | 齐鲁工业大学 | A kind of hollow nickel molybdate nano flower assembled by nanometer sheet and preparation method thereof |
| CN109012683A (en) * | 2018-08-09 | 2018-12-18 | 扬州大学 | A kind of preparation method of cobalt molybdate tiny balloon elctro-catalyst |
| CN109663590A (en) * | 2018-12-29 | 2019-04-23 | 泉州师范学院 | It is a kind of using egg shell as catalysis material of reactor and the preparation method and application thereof |
| CN110040779A (en) * | 2019-05-05 | 2019-07-23 | 河南师范大学 | A kind of preparation method of calcium molybdate luminescent material |
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| SU432100A1 (en) * | 1972-11-29 | 1974-06-15 | Ю. К. Целинский, М. В. Мохосоев , И. И. Сомова | |
| RU2049068C1 (en) * | 1992-12-31 | 1995-11-27 | Вячеслав Андреевич Патрушев | Process for preparing calcium molybdate |
| US5585077A (en) * | 1995-08-03 | 1996-12-17 | Arco Chemical Technology, L.P. | Molybdenum epoxidation catalyst recovery |
| US5776848A (en) * | 1997-07-30 | 1998-07-07 | Arco Chemical Technology, L.P. | Molybdenum epoxidation catalyst recovery |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717120B (en) * | 2009-12-14 | 2011-08-03 | 上海应用技术学院 | Solvent thermal induction control synthesis method for nano molybdate with scheelite structure |
| CN105470489A (en) * | 2016-01-11 | 2016-04-06 | 福建师范大学泉港石化研究院 | Preparation method of MoO2 hollow microsphere material for high-performance lithium ion battery |
| CN105470489B (en) * | 2016-01-11 | 2019-04-16 | 福建师范大学泉港石化研究院 | High performance lithium ion battery MoO2The preparation method of hollow microsphere material |
| CN107651713A (en) * | 2017-11-14 | 2018-02-02 | 齐鲁工业大学 | A kind of hollow nickel molybdate nano flower assembled by nanometer sheet and preparation method thereof |
| CN107651713B (en) * | 2017-11-14 | 2019-03-19 | 齐鲁工业大学 | A kind of hollow nickel molybdate nano flower and preparation method thereof by nanometer sheet assembling |
| CN109012683A (en) * | 2018-08-09 | 2018-12-18 | 扬州大学 | A kind of preparation method of cobalt molybdate tiny balloon elctro-catalyst |
| CN109012683B (en) * | 2018-08-09 | 2021-05-14 | 扬州大学 | Preparation method of cobalt molybdate hollow microsphere electrocatalyst |
| CN109663590A (en) * | 2018-12-29 | 2019-04-23 | 泉州师范学院 | It is a kind of using egg shell as catalysis material of reactor and the preparation method and application thereof |
| CN110040779A (en) * | 2019-05-05 | 2019-07-23 | 河南师范大学 | A kind of preparation method of calcium molybdate luminescent material |
| CN110040779B (en) * | 2019-05-05 | 2021-07-13 | 河南师范大学 | Preparation method of calcium molybdate luminescent material |
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