CN104860353B - A kind of preparation method of the molybdic acid cadmium hollow ball assembled by nano-particle - Google Patents
A kind of preparation method of the molybdic acid cadmium hollow ball assembled by nano-particle Download PDFInfo
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- CN104860353B CN104860353B CN201510180985.5A CN201510180985A CN104860353B CN 104860353 B CN104860353 B CN 104860353B CN 201510180985 A CN201510180985 A CN 201510180985A CN 104860353 B CN104860353 B CN 104860353B
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Abstract
The invention belongs to field of material technology, the preparation method being specifically related to a kind of molybdic acid cadmium hollow ball assembled by nano-particle.Described preparation method mainly comprises the steps for preparing sodium molybdate solution, cadmium sulfate solution and sodium carbonate liquor respectively, then joins in prepared cadmium sulfate solution by prepared sodium molybdate solution, obtains a mixture system with white precipitate after rocking.Described mixture system is joined in prepared sodium carbonate liquor and rocks standing, obtain thick product.By described thick product separating, washing and namely obtain target product after drying.Present invention process is simple, and the obtained molybdic acid cadmium hollow ball assembled by nano-particle has photocatalysis and adsorption dual function, can be used for field of environment protection.
Description
Technical field
The invention belongs to field of material technology, the preparation method being specifically related to a kind of molybdic acid cadmium hollow ball assembled by nano-particle.
Background technology
Since the second half in 20th century, people strengthen gradually for the consciousness of environmental conservation.Organic dyestuff also becomes the main source that water pollution is very important while bringing the world of people's riot of color, and health of people impact is great.For eliminating as much as its negative effect, scientists study goes out photocatalytic method and two kinds of typical processing methods of absorption method.
Light is absorbed by photocatalytic method mainly by nano level semi-conducting material, produces electron-hole pair, and mineralizing and degrading dyestuff carries out water pollution process.But, in a lot of situations, people to apply photocatalytic method and carry out water pollution and process and need to face a comparatively severe problem, it may be assumed that nano-scale photocatalyst excessively disperses, and granule is little, is not readily separated.
And absorption method is usually the high-specific surface area utilizing the loose structure of adsorbing material to have to carry out water pollution process.But, absorption method is compared to photocatalytic method, it is impossible to thoroughly decomposing organic matter.
It is known that molybdic acid cadmium is a based semiconductor material, ultra violet applications can be absorbed in photocatalysis field.If nano level molybdic acid cadmium granule is assembled into hollow-core construction, the photocatalysis property of cadmium molybdate nano ball can not only be kept, and the hollow-core construction being assembled into has large specific surface area, adsorbable more organic dyestuff, contribute to strengthening photo-catalysis function.
Under the guiding of this thinking, research and develop a kind of material with absorption and photocatalysis dual-use function and have important practical significance.
Summary of the invention
An object of the present invention is in that for the deficiencies in the prior art, research and develop and a kind of there is absorption and the material of photocatalysis dual-use function, described in there is the material of absorption and photocatalysis dual-use function adopt solution at room temperature method and obtain by your moral ripening (OstwaldRipening) mechanism preparation of Oswald.
The preparation method that the present invention provides a kind of molybdic acid cadmium hollow ball assembled by nano-particle, comprises the steps:
Step 1: with deionized water for solvent, compound concentration is the sodium molybdate solution of 0.1mol/L.
Step 2: with deionized water for solvent, compound concentration is the cadmium sulfate solution of 0.1～0.4mol/L.
Step 3: with deionized water for solvent, compound concentration is the sodium carbonate liquor of 0.3mol/L.
Step 4: measure the sodium molybdate solution obtained in step 1 and join in the cadmium sulfate solution obtained in step 2, obtains a mixture system with white precipitate after rocking certain time.
Step 5: joined by the mixture system obtained in step 4 in the diluent of the sodium carbonate liquor obtained in step 3, stands after rocking certain time, obtains thick product.
Step 6: the thick product obtained in step 5 is centrifuged, washs, namely obtains target product after drying.
Saying further, the purity of medicine sodium molybdate described in step 1～3, cadmium sulfate and sodium carbonate is not less than chemical pure.
Saying further, in the mixture system obtained in described step 4, molybdenum acid ion is 1.5:1 with the ratio of the amount of substance of cadmium ion.
Saying further, the time of rocking in described step 4 is less than 15s.
Saying further, in the thick product obtained in described step 5, carbanion is 1:1 with the ratio of the amount of substance of molybdenum acid ion.
Saying further, the time of rocking in described step 5 is 5～20s, and time of repose is 1～20h.
Saying further, the concrete operations of described step 6 are after being centrifuged by the thick product obtained in step 5, adopt the alternately washing of deionized water, dehydrated alcohol, acetone, namely obtain target product after drying.
Furthermore, described deionized water, dehydrated alcohol, acetone consumption be with washing leaching cake for mark, the mass ratio of deionized water, dehydrated alcohol, acetone and washing leaching cake is 20:20:20:1.
Furthermore, described alternately washing times is 3～6 times.
Furthermore, described baking temperature is 60～80 DEG C, and drying time is 4～8h.
The beneficial effects of the present invention is:
1, present invention achieves and obtain, in solution blending mode, the molybdic acid cadmium hollow ball that is assembled into by nano-particle under room temperature, the Inorganic synthese for nano material provides a kind of new route of synthesis.
2, the present invention adopts simply common chemical drugs to be precursors, does not produce by-product in preparation process, and environmental pollution is little, is a kind of environment-friendly type synthesis technique.
3, the present invention controls hollow ball size by regulating the concentration of solution, and solvent materials is easy to get, and solution concentration is easily adjusted, and products therefrom is easily separated, good dispersion.
4, the present invention does not use any organic additive or surfactant, it is not necessary to other heating or hydro-thermal, simplifies the operating procedure of hydro-thermal reaction etc., makes technique simpler, it is simple to industrial operation.
In brief, present invention process is simple, and whole preparation system easily builds, and easy and simple to handle, condition is easily-controllable, with low cost, and target product pattern is homogeneous, and size is easily-controllable, and purity is high, better crystallinity degree, processes convenient succinct, is suitable for industrial mass production.And target product has the excellent properties of nano material, irradiation under ultraviolet ray is sensitive, can photocatalytically degradating organic dye.Meanwhile, molybdic acid cadmium granule is assembled into hollow ball, there is bigger specific surface area, there is good adsorption function, especially that the adsorption effect of organic dyestuff is very good, be conducive to the realization of photo-catalysis function.The hollow ball that the present invention prepares has photocatalysis and adsorption dual function, can be used for field of environment protection.
Accompanying drawing explanation
Fig. 1 show the structural characterization figure of the molybdic acid cadmium hollow ball assembled by nano-particle that the method for the invention prepares.
Wherein, (a) is XRD figure, and (b) schemes for FE-SEM.
Fig. 2 show the FE-SEM figure of the embodiment of the present invention 1～4 products therefrom.
Wherein (a) schemes for embodiment 1 products obtained therefrom FE-SEM, and (b) schemes for embodiment 2 products obtained therefrom FE-SEM, and (c) schemes for embodiment 3 products obtained therefrom FE-SEM, and (d) schemes for embodiment 4 products obtained therefrom FE-SEM.
Detailed description of the invention
The preparation method that the present invention provides a kind of molybdic acid cadmium hollow ball assembled by nano-particle, comprises the steps:
Step 1: with deionized water for solvent, compound concentration is the sodium molybdate solution of 0.1mol/L.
Step 2: with deionized water for solvent, compound concentration is the cadmium sulfate solution of 0.1～0.4mol/L.
Step 3: with deionized water for solvent, compound concentration is the sodium carbonate liquor of 0.3mol/L.
Step 4: measure the sodium molybdate solution obtained in step 1 and join in the cadmium sulfate solution obtained in step 2, obtains a mixture system with white precipitate after rocking certain time.
Step 5: joined by the mixture system obtained in step 4 in the diluent of the sodium carbonate liquor obtained in step 3, stands after rocking certain time, obtains thick product.
Step 6: the thick product obtained in step 5 is centrifuged, washs, namely obtains target product after drying.
Saying further, the purity of medicine sodium molybdate described in step 1～3, cadmium sulfate and sodium carbonate is not less than chemical pure.
Saying further, in the mixture system obtained in described step 4, molybdenum acid ion is 1.5:1 with the ratio of the amount of substance of cadmium ion.
Saying further, the time of rocking in described step 4 is less than 15s.
Saying further, in the thick product obtained in described step 5, carbanion is 1:1 with the ratio of the amount of substance of molybdenum acid ion.
Saying further, the time of rocking in described step 5 is 5～20s, and time of repose is 1～20h.
Saying further, the concrete operations of described step 6 are after being centrifuged by the thick product obtained in step 5, adopt the alternately washing of deionized water, dehydrated alcohol, acetone, namely obtain target product after drying.
Furthermore, described deionized water, dehydrated alcohol, acetone consumption be with washing leaching cake for mark, the mass ratio of deionized water, dehydrated alcohol, acetone and washing leaching cake is 20:20:20:1.
Furthermore, described alternately washing times is 3～6 times.
Furthermore, described baking temperature is 60～80 DEG C, and drying time is 4～8h.
Describe the present invention below in conjunction with specific embodiment and accompanying drawing.It should be noted that, what the combination of technical characteristic described in following embodiment or technical characteristic was not construed as isolating, they can be mutually combined thus reaching superior technique effect.
Embodiment 1
Preparing sodium molybdate solution concentration is 0.1mol/L, and cadmium sulfate solution concentration is 0.4mol/L, gained molybdic acid cadmium hollow ball when sodium carbonate liquor volume is 13mL after dilution.
Preparation method:
(1) in the centrifuge tube that scale is 10mL, add the cadmium sulfate solution of 1mL0.4mol/L, then the sodium molybdate solution of 6mL0.1mol/L is poured in described cadmium sulfate solution, after somewhat rocking, obtain white suspension.
(2) white suspension in centrifuge tube is distributed in the 13mL sodium carbonate liquor being loaded in 50mL beaker (wherein, the amount of substance of sodium carbonate is 0.0006mol), stands 1 hour after somewhat rocking.Precipitated product after standing is transferred to centrifugation in centrifuge tube, alternately use deionized water, dehydrated alcohol and acetone (wherein, deionized water, dehydrated alcohol, acetone consumption be: with washing leaching cake for mark, deionized water, dehydrated alcohol, acetone consumption are its 20 times respectively) washing 3 times respectively, after having washed every time, centrifugation.Namely final gained centrifugal sediment dry 4h at 80 DEG C obtains target product.
Fig. 1 show the structural characterization figure of the molybdic acid cadmium hollow ball assembled by nano-particle that the method for the invention prepares, and wherein, (a) is XRD figure, and (b) schemes for FE-SEM.The X-ray powder diffraction pattern of the present embodiment products therefrom is substantially identical with Fig. 1's (a), therefore does not repeat to list, and gained peak is the diffraction maximum of molybdic acid cadmium crystal.Fig. 2 (a) show field emission scanning electron microscope (FE-SEM) photo of the present embodiment product, and the hollow ball that the nano-particle that products therefrom is tiny as seen from the figure is assembled into, its size is at 400～600nm.
Embodiment 2
Preparing sodium molybdate solution concentration is 0.1mol/L, and cadmium sulfate solution concentration is 0.2mol/L, gained molybdic acid cadmium hollow ball when sodium carbonate liquor volume is 12mL after dilution.
Preparation method:
(1) in the centrifuge tube that scale is 10mL, add the cadmium sulfate solution of 2mL0.2mol/L, then pour the sodium molybdate solution of 6mL0.1mol/L into described cadmium sulfate solution, after somewhat rocking, obtain white suspension.
(2) white suspension in centrifuge tube is distributed in the 12mL sodium carbonate liquor being loaded in 50mL beaker (wherein, the amount of substance of sodium carbonate is 0.0006mol), stands 1 hour after somewhat rocking.Precipitated product after standing is transferred to centrifugation in centrifuge tube, alternately use deionized water, dehydrated alcohol and acetone (wherein, deionized water, dehydrated alcohol, acetone consumption be: with washing leaching cake for mark, deionized water, dehydrated alcohol, acetone consumption are its 20 times respectively) washing 3 times respectively, after having washed every time, centrifugation, namely final gained centrifugal sediment dry 8h at 60 DEG C obtains target product.
The X-ray powder diffraction pattern of the present embodiment products therefrom is substantially identical with Fig. 1's (a), therefore does not repeat to list, and gained peak is the diffraction maximum of molybdic acid cadmium crystal.Fig. 2 (b) show field emission scanning electron microscope (FE-SEM) photo of the present embodiment product, the hollow ball that the nano-particle that product is tiny as seen from the figure is assembled into, and its size is at 500～1000 nanometers.
Embodiment 3
Preparing sodium molybdate solution concentration is 0.1mol/L, and cadmium sulfate solution concentration is 0.133mol/L, gained molybdic acid cadmium hollow ball when sodium carbonate liquor volume is 11mL after dilution.
Preparation method:
(1) in the centrifuge tube that scale is 10mL, add the cadmium sulfate solution of 3mL0.133mol/L, then pour the sodium molybdate solution of 6mL0.1mol/L into described cadmium sulfate solution, after somewhat rocking, obtain white suspension.
(2) white suspension in centrifuge tube is distributed in the 11mL sodium carbonate liquor being loaded in 50mL beaker (wherein, the amount of substance of sodium carbonate is 0.0006mol), stands 1 hour after somewhat rocking.Precipitated product after standing is transferred to centrifugation in centrifuge tube, alternately use deionized water, dehydrated alcohol and acetone (wherein, deionized water, dehydrated alcohol, acetone consumption be: with washing leaching cake for mark, deionized water, dehydrated alcohol, acetone consumption are its 20 times respectively) washing 3 times respectively, after having washed every time, centrifugation, namely final gained centrifugal sediment dry 6h at 60 DEG C obtains target product
The X-ray powder diffraction pattern of the present embodiment products therefrom is substantially identical with Fig. 1's (a), therefore does not repeat to list, and gained peak is the diffraction maximum of molybdic acid cadmium crystal.Fig. 2 (c) show field emission scanning electron microscope (FE-SEM) photo of the present embodiment product, the hollow ball that the nano-particle that product is tiny as seen from the figure is assembled into, and its size is at 1000～1500 nanometers.
Embodiment 4
Preparing sodium molybdate solution concentration is 0.1mol/L, and cadmium sulfate solution concentration is 0.1mol/L, gained molybdic acid cadmium hollow ball when sodium carbonate liquor volume is 10mL after dilution.
Preparation method:
(1) in the centrifuge tube that scale is 10mL, add the cadmium sulfate solution of 4mL0.1mol/L, then pour the sodium molybdate solution of 6mL0.1mol/L into described cadmium sulfate solution, after somewhat rocking, obtain white suspension.
(2) white suspension in centrifuge tube is distributed in the 10mL sodium carbonate liquor being loaded in 50mL beaker (wherein, the amount of substance of sodium carbonate is 0.0006mol), stands 1 hour after somewhat rocking.Precipitated product after standing is transferred to centrifugation in centrifuge tube, alternately use deionized water, dehydrated alcohol and acetone (wherein, deionized water, dehydrated alcohol, acetone consumption be: with washing leaching cake for mark, deionized water, dehydrated alcohol, acetone consumption are its 20 times respectively) washing 3 times respectively, after having washed every time, centrifugation, namely final gained centrifugal sediment dry 6h at 70 DEG C obtains target product.
The X-ray powder diffraction pattern of the present embodiment products therefrom is substantially identical with Fig. 1's (a), therefore does not repeat to list, and gained peak is the diffraction maximum of molybdic acid cadmium crystal.Fig. 2 (d) show field emission scanning electron microscope (FE-SEM) photo of the present embodiment product, and the hollow ball that the nano-particle that product is tiny as seen from the figure is assembled into, its size is at 1500 ran.
Present invention process is simple, and obtained target product has the excellent properties of nano material, and irradiation under ultraviolet ray is sensitive, can photocatalytically degradating organic dye.Meanwhile, molybdic acid cadmium granule is assembled into hollow ball, there is bigger specific surface area, there is good adsorption function, especially that the adsorption effect of organic dyestuff is very good, be conducive to the realization of photo-catalysis function.The hollow ball that the present invention prepares has photocatalysis and adsorption dual function, can be used for field of environment protection.
Although have been presented for some embodiments of the present invention herein, it will be appreciated by those of skill in the art that without departing from the spirit of the invention, it is possible to the embodiments herein is changed.Above-described embodiment is illustrative of, should restriction using the embodiments herein as interest field of the present invention.
Claims (6)
1. the preparation method of the molybdic acid cadmium hollow ball that a kind is assembled by nano-particle, it is characterised in that by carbanion (CO3 2-) with molybdic acid cadmium suspension effect, promote Ostwald ripening to obtain that pattern is homogeneous, granular size is controlled, high-purity, process is convenient, have photocatalysis and adsorption dual function, the molybdic acid cadmium hollow ball that assembled by nano-particle, comprise the steps:
Step 1: with deionized water for solvent, compound concentration is the sodium molybdate solution of 0.1mol/L；
Step 2: with deionized water for solvent, compound concentration is the cadmium sulfate solution of 0.1～0.4mol/L；
Step 3: with deionized water for solvent, compound concentration is the sodium carbonate liquor of 0.3mol/L；
Step 4: measure the sodium molybdate solution obtained in step 1 and join in the cadmium sulfate solution obtained in step 2, the ratio of molybdenum acid ion and the amount of substance of cadmium ion is 1.5:1, rocks the time less than obtaining a molybdic acid cadmium suspension with white precipitate after 15s；
Step 5: the molybdic acid cadmium suspension obtained in step 4 is joined in the diluent of the sodium carbonate liquor obtained in step 3, the time of rocking is 5～20s, time of repose is 1～20h, obtain thick product, wherein, in the sodium molybdate solution obtained in carbanion and the described step 1 measured in the diluent of described sodium carbonate liquor, the ratio of the amount of substance of molybdenum acid ion is 1:1；
Step 6: the thick product obtained in step 5 is centrifuged, washs, namely obtains target product after drying.
2. the preparation method of a kind of molybdic acid cadmium hollow ball assembled by nano-particle as claimed in claim 1, it is characterised in that the purity of sodium molybdate described in step 1～3, cadmium sulfate and sodium carbonate is not less than chemical pure.
3. the preparation method of a kind of molybdic acid cadmium hollow ball assembled by nano-particle as claimed in claim 1, it is characterized in that, the concrete operations of described step 6 are after being centrifuged by the thick product obtained in step 5, adopt the alternately washing of deionized water, dehydrated alcohol, acetone, namely obtain target product after drying.
4. the preparation method of a kind of molybdic acid cadmium hollow ball assembled by nano-particle as claimed in claim 3, it is characterized in that, described deionized water, dehydrated alcohol, acetone consumption be with washing leaching cake for mark, the mass ratio of deionized water, dehydrated alcohol, acetone and washing leaching cake is 20:20:20:1.
5. the preparation method of a kind of molybdic acid cadmium hollow ball assembled by nano-particle as claimed in claim 3, it is characterised in that described alternately washing times is 3～6 times.
6. the preparation method of a kind of molybdic acid cadmium hollow ball assembled by nano-particle as claimed in claim 3, it is characterised in that described baking temperature is 60～80 DEG C, and drying time is 4～8h.
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| CN109336178B (en) * | 2018-12-06 | 2020-12-08 | 洛阳理工学院 | Preparation method of cadmium molybdate dendritic crystal |
Citations (2)
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| CN101665269A (en) * | 2009-08-31 | 2010-03-10 | 广西民族大学 | Preparation method of cadmium molybdate octahedron with controllable grain size |
| CN103833080A (en) * | 2014-03-25 | 2014-06-04 | 洛阳理工学院 | Preparation method for cadmium molybdate porous spheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101665269A (en) * | 2009-08-31 | 2010-03-10 | 广西民族大学 | Preparation method of cadmium molybdate octahedron with controllable grain size |
| CN103833080A (en) * | 2014-03-25 | 2014-06-04 | 洛阳理工学院 | Preparation method for cadmium molybdate porous spheres |
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| CdMoO4微球的微波辅助法快速合成及其光催化性能;张大凤等;《材料导报》;20110531;第25卷;第81-83页 * |
| Room Temperature Synthesis of Hollow CdMoO4 Microspheres by a Surfactant-Free Aqueous Solution Route;Wen-Shou Wang et al.;《The Journal of Physical Chemistry B》;20061013;第110卷;第23154-23158页 * |
| Template-Free Fabrication of CdMoO4 Hollow Spheres and Their Morphology-Dependent Photocatalytic Property;Lin Zhou et al.;《Crystal Growth and Design》;20080829;第8卷(第10期);第3695页摘要、第3696页第2部分实验部分 * |
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