CN100528755C - Plum-blossom-like multicrystal-state nano zinc-oxide purticles and its preparing method - Google Patents
Plum-blossom-like multicrystal-state nano zinc-oxide purticles and its preparing method Download PDFInfo
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- CN100528755C CN100528755C CNB2007100196731A CN200710019673A CN100528755C CN 100528755 C CN100528755 C CN 100528755C CN B2007100196731 A CNB2007100196731 A CN B2007100196731A CN 200710019673 A CN200710019673 A CN 200710019673A CN 100528755 C CN100528755 C CN 100528755C
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Abstract
The invention relates to a mume flower shaped polycrystalline state nanometer white zinc particle and the manufacturing method. It includes the following steps: whisking zinc stearate and 80-100 times mol quantity of octadecene in inert atmosphere, heating to 260-280 degree centigrade at the speed of 0.5-5 degree centigrade per minute; dropping hydrogen peroxide at 3-6 drops per second, keeping temperature for 2-4 hours, purifying raw product to gain mume flower shaped polycrystalline state nanometer white zinc. The distance between brim of petal and center is 12-15nm, and the diameter of the particle is 30+/-5nm. It has excellent optical property. And the product has widely application prospects in biology fluorescence labeling and medicine carrying.
Description
Technical field:
The invention belongs to the nanometer grain preparation method technical field, particularly polycrystalline state zinc oxide of plum blossom shape nanostructure and preparation method thereof.
Background technology:
Nano zine oxide is a kind of novel inorganic functional material, all have property at aspects such as optics, electricity, catalysis, mechanics, be widely used in coating, rubber, gas sensor, chemical sensor, voltage dependent resistor, ultraviolet shielded, catalyzer, sterilant, biology, medicine and other fields.Nano zinc oxide material has caused more and more scholars' interest in recent years, particularly for the preparation and the control of various different shape zinc oxide nanostructures." American Chemical Society can will " (Journal of the American Chemical Society for example, 127,13331-13337 2005) reported the preparation method of the spherical and pyramid nanostructure (20～30 nanometer) of zinc oxide, because the coordination ability of the 1-octadecyl phosphoric acid as surface ligand (1-octadecanal phosphoric acid) that is adopted is very strong, can just be combined in the surface of zinc oxide at the zinc oxide crystalline initial stage, when not having competent oxygen source, zinc oxide can not further growth, can only obtain pyramid or spheric nano particle.(Aav.Mater 17 for Germany's " high material ", 1873-1877,2005) preparation method of Bao Dao zinc oxide pyramid nanostructure (about 100 nanometers), adopt tetradecyl phosphoric acid (tetradecylphosphonic acid), trioctyl-phosphine oxide (trioctyphosphine oxide) and cetylamine (1-hexadexylamine) as surface ligand, because these three kinds of surface ligands are active different to each crystal face in the zinc oxide growth, the binding ability difference is so be grown to serve as bigger pyramid pattern.Since the surface ligand that prior art adopts to the crystal coordination ability or strong or a little less than, and can not provide sufficient active oxygen source, so all can not get the nano zine oxide of flower-like structure.
Summary of the invention:
The purpose of this invention is to provide a kind of plum-blossom-like multicrystal-state nano zinc-oxide purticles and preparation method thereof, to overcome the above-mentioned shortcoming of prior art.
The preparation method of plum-blossom-like multicrystal-state nano zinc-oxide purticles of the present invention is characterized in that: octadecylene temperature rise rate with 0.5 ℃/minute～5 ℃/minute under inert atmosphere and stirring of Zinic stearas and 80～100 times of molar weights is warming up to 260～280 ℃; Splash into the hydrogen peroxide of 15～20 times of Zinic stearas molar weights with 3～6 droplets/second speed, 260～280 ℃ of insulations 2～4 hours; Crude product is purified, promptly obtain the polycrystalline Nano zinc oxide of plum blossom shape structure.
This product can be dispersed in the toluene and be preserved.
Plum-blossom-like multicrystal-state nano zinc-oxide purticles of the present invention, be characterised in that its essentially consist unit is a plum blossom shape polycrystalline Nano zinc oxide, its petal edge is 12～15 nanometers to petal width between centers, and the diameter of plum-blossom-like multicrystal-state nano zinc-oxide purticles is in 30 ± 5 nanometers, and petal is evenly distributed.
The inventive method is with the different of prior art: because present method is to utilize the reaction of double-basis, promptly hydrogen peroxide participates in reaction,, only needs can finish reaction once going on foot as solvent and surface ligand with octadecylene; Reactant among the present invention is relatively cheap, and method is simpler; The flower shape zinc oxide nanostructure is not appeared in the newspapers so far as yet.The plum-blossom-like multicrystal-state nano zinc-oxide purticles that the inventive method prepares is smaller, the petal edge is 12～15 nanometers to petal width between centers, the diameter of plum-blossom-like multicrystal-state nano zinc-oxide purticles is in 30 ± 5 nanometers, owing to be petal-like, so surface area ratio is bigger, can be used as micromolecular sorbent material, have stronger medicine carrying ability, these characteristics make it at molecule sensor and biological medicine carrying field profound application prospect be arranged.
Description of drawings:
Fig. 1 is the transmission electron microscope photo of the embodiment of the invention 1 product plum blossom shape polycrystalline Nano zinc oxide;
Fig. 2 is the high-resolution-ration transmission electric-lens photo of plum blossom shape polycrystalline Nano zinc oxide;
Fig. 3 is the X ray energy dispersive spectrogram of plum blossom shape polycrystalline Nano zinc oxide.
Fig. 4 is the electron diffraction photo of plum blossom shape polycrystalline Nano zinc oxide;
Fig. 5 is the abosrption spectrogram of plum blossom shape polycrystalline Nano zinc oxide;
Fig. 6 is the fluorogram of plum blossom shape polycrystalline Nano zinc oxide.
Fig. 7 is the transmission electron microscope photo of embodiment 2 product plum blossom shape polycrystalline Nano zinc oxide;
Fig. 8 is the high-resolution-ration transmission electric-lens photo of embodiment 2 product plum blossom shape polycrystalline Nano zinc oxide.
Fig. 9 is the transmission electron microscope photo of embodiment 3 product plum blossom shape polycrystalline Nano zinc oxide;
Figure 10 is the high-resolution-ration transmission electric-lens photo of embodiment 3 product plum blossom shape polycrystalline Nano zinc oxide.
Figure 11 is the transmission electron microscope photo of product in the comparative example.
Embodiment:
Embodiment 1: the preparation plum-blossom-like multicrystal-state nano zinc-oxide purticles.
Weighing 126.5mg (0.2mmol) Zinic stearas and 4.45g (16mmol) octadecylene, these two kinds of precursors are put into the three-necked flask that capacity is 25ml, middle a bite with rubber stopper beyond the Great Wall, insert thermometer at the stopper mesopore, slowly be warming up to 260 ℃ by average 0.5 ℃/minute under nitrogen atmosphere, the interior solution of bottle is clarified all the time in the process; Splash into 2ml (3mmol) hydrogen peroxide with 3～6 droplets/second speed, in 260 ℃ of insulations 2 hours, after treating muddy yellow substance to occur in the bottle, reaction finished.Crude product is scattered in the toluene, with 3000rpm centrifugal 15 minutes, toluene by volume in the clear liquid that obtains: ethanol=1: 5 adds ethanol, with 3000rpm centrifugal 15 minutes, the precipitation that obtains was disperseed with 2mL toluene, adds 10mL ethanol then, centrifugal, the precipitation that obtains centrifugal again 3 times according to the methylbenzene methanol consumption of back is dispersed in the throw out that obtains in the toluene at last, obtains colourless solution.
Above-mentioned solution is dripped 2～3 drips on the plating carbon film copper mesh that testing electronic microscope uses, treat that solvent volatilizees fully after, the plating carbon film copper mesh that is loaded with product put under acceleration voltage is 200,000 volts JOEL2100 type high resolution transmission electron microscopy takes pictures.From resulting transmission electron microscope photo Fig. 1, the diameter of visible plum-blossom-like multicrystal-state nano zinc-oxide purticles is 30 ± 5 nanometers.
Fig. 2 is the high resolution picture of zinc oxide plum blossom shape nanostructure, and visible its structure is the plum blossom shape from this figure, and the petal edge is 12～15 nanometers to the distance at petal center, and can see lattice fringe clearly.
Fig. 3 is its X ray energy dispersive analysis chart, by curve A in the comparison diagram 3 and standard oxidation zinc X ray energy dispersive analysis chart collection of illustrative plates, has proved that its composition is a zinc oxide, and has marked each crystal plane direction.
Fig. 4 is an electron-diffraction diagram, from the visible diffraction ring corresponding with each crystal plane direction of Fig. 3 of Fig. 4.
Fig. 5 is its abosrption spectrogram, and curve C is that the absorption peak of zinc oxide plum blossom shape nanostructure is in 354 nanometers from Fig. 5.
Fig. 6 has provided the fluorogram of plum blossom shape polycrystalline Nano zinc oxide.From Fig. 6, get visible its main glow peak of curve B in 375 nanometers.
As from the foregoing, the product that present embodiment prepares is a plum blossom shape multicrystal-state nano zinc-oxide, its essentially consist unit is a plum blossom shape polycrystalline Nano Zinc oxide particles, its petal edge is 12～15 nanometers to petal width between centers, the diameter of plum blossom shape polycrystalline Nano Zinc oxide particles is 30 ± 5 nanometers, and petal is evenly distributed, and its absorption peak is 354 nanometers, and the fluorescence radiation peak value is 375 nanometers.
Embodiment 2: the ratio of conditioned reaction thing, temperature of reaction and temperature rise rate prepare plum-blossom-like multicrystal-state nano zinc-oxide purticles.
126.5mg (0.2mmol) Zinic stearas and 5.04g (20mmol) octadecylene are placed three-necked flask, slowly be warming up to 280 ℃ by average 5 ℃/minute speed under nitrogen atmosphere, the interior solution of bottle is clarified all the time in the whole process; Splash into 2.7ml (4mmol) hydrogen peroxide with 3～6 droplets/second speed then, in 280 ℃ of insulations 2 hours, after treating muddy yellow substance to occur in the bottle, reaction finished.Crude product is scattered in the toluene, with 3000rpm centrifugal 15 minutes, toluene by volume in the clear liquid that obtains: ethanol=1: 5 adds ethanol, centrifugal 15 minutes again with 3000rpm, the precipitation that obtains is disperseed with 2mL toluene, adds 10mL ethanol, and is centrifugal, the precipitation that obtains centrifugal again 3 times according to the methylbenzene methanol consumption of back obtains colourless solution in the middle of at last the precipitation that obtains being dispersed in toluene.
Above-mentioned solution is dripped 2～3 drips on the plating carbon film copper mesh that testing electronic microscope uses, treat that solvent volatilizees fully after, the plating carbon film copper mesh that is loaded with product put under acceleration voltage is 200,000 volts JOEL2100 type high resolution transmission electron microscopy takes pictures.From resulting transmission electron microscope photo Fig. 7, the diameter of visible plum blossom shape polycrystalline Nano Zinc oxide particles is in 30 ± 2 nanometers.Fig. 8 is the high resolution picture of this zinc oxide plum blossom shape nanostructure, and visible its structure is the plum blossom shape from this figure, and the petal edge is 12～15 nanometers to the distance at petal center, and can see lattice fringe clearly.
As from the foregoing, the product that present embodiment prepares is a plum blossom shape multicrystal-state nano zinc-oxide, its essentially consist unit is a plum blossom shape polycrystalline Nano Zinc oxide particles, its petal edge is 12～15nm to petal width between centers, the diameter of plum blossom shape polycrystalline Nano Zinc oxide particles is in 30 ± 2 nanometers, and petal is evenly distributed.
Embodiment 3: the ratio of conditioned reaction thing, and temperature of reaction, soaking time, and temperature rise rate prepares plum-blossom-like multicrystal-state nano zinc-oxide purticles.
126.5mg (0.2mmol) Zinic stearas and 4.70g (18.6mmol) octadecylene are put into three-necked flask, speed by 3 ℃/minute under nitrogen atmosphere slowly is warming up to 270 ℃, splash into 2.8ml (4.15mmol) hydrogen peroxide with 3～6 droplets/second speed, in 270 ℃ of insulations 4 hours, after muddy yellow substance occurring in the bottle, reaction finishes.Crude product is scattered in the toluene, with 3000rpm centrifugal 15 minutes, toluene by volume in the clear liquid that obtains: ethanol=1: 5 adds ethanol, centrifugal 15 minutes again with 3000rpm, the precipitation that obtains is disperseed with 2mL toluene, adds 10mL ethanol, and is centrifugal, the precipitation that obtains centrifugal again 3 times according to the methylbenzene methanol consumption of back is dispersed in the precipitation that obtains at last and obtains colourless solution in the toluene.
Above-mentioned solution is dripped 2～3 drips on the plating carbon film copper mesh that testing electronic microscope uses, treat that solvent volatilizees fully after, the plating carbon film copper mesh that is loaded with product put under acceleration voltage is 200,000 volts JOEL2100 type high resolution transmission electron microscopy takes pictures.From transmission electron microscope photo Fig. 9 of resulting zinc oxide plum blossom shape nanostructure, visible plum blossom shape polycrystalline Nano Zinc oxide particles is in 30 ± 4 nanometers.
Figure 10 is the high resolution picture of zinc oxide plum blossom shape nanostructure, and visible its structure is the plum blossom shape from this figure, and the petal edge is 13～15 nanometers to the distance at petal center, and can see lattice fringe clearly.
As from the foregoing, the product that present embodiment prepares is a plum-blossom-like multicrystal-state nano zinc-oxide purticles, its essentially consist unit is a plum blossom shape polycrystalline Nano Zinc oxide particles, its petal edge is 13～15 nanometers to petal width between centers, the diameter of plum blossom shape polycrystalline Nano Zinc oxide particles is in 30 ± 4 nanometers, and petal is evenly distributed.
From above embodiment of the invention presentation of results, as solvent and surface ligand and have under the situation that hydrogen peroxide participates in, the ratio by the conditioned reaction thing has obtained plum blossom shape polycrystalline Nano zinc oxide structure at octadecylene.
Below do not have hydrogen peroxide to participate in the situation of reaction by one group of comparative example explanation.
Comparative example: do not have hydrogen peroxide to participate in the product that obtains under the response situation
Step is: cancellation splashes into the step of hydrogen peroxide among the embodiment 1, and other are operated fully with embodiment 1, obtain transparent final product, and purification process is fully with embodiment 1, the product that obtains is dispersed in obtains colourless solution in the toluene.
Above-mentioned solution is dripped 2～3 drips on the plating carbon film copper mesh that testing electronic microscope uses, treat that solvent volatilizees fully after, the plating carbon film copper mesh that is loaded with product put under acceleration voltage is 200,000 volts JOEL2100 type high resolution transmission electron microscopy takes pictures.Figure 11 is its transmission electron microscope photo, and big or small as can be seen inhomogeneous from photo, the nano particle that pattern differs presents the reunion shape.As seen do not having hydrogen peroxide to participate in can not get the zinc oxide flower-like nanostructure under the situation of reaction, can only obtain that pattern differs and uneven structure.
The analysis-by-synthesis explanation:
In reaction of the present invention, octadecylene is to participate in reaction as solvent and surface ligand, participates in reaction owing to added hydrogen peroxide, and the sufficient activity oxygen source is provided, thus zinc oxide can grow fully, to reaching thermodynamic(al)equilibrium; Octadecylene can active oxidation zinc some specific crystal face, cause the preferred growth of some crystal face, thereby obtain plum blossom shape structure.Under the situation that does not have hydrogen peroxide to participate in, owing to do not have sufficient active oxygen source, so can not get the zinc oxide of plum blossom shape structure.The feeding rare gas element can be got rid of the air in the reaction vessel, and the water vapour that produces after the hydrogen peroxide decomposition, and the inert atmosphere of Cai Yonging is a nitrogen in the present embodiment.
Claims (2)
1, a kind of preparation method of plum-blossom-like multicrystal-state nano zinc-oxide purticles is characterized in that: octadecylene temperature rise rate with 0.5 ℃/minute～5 ℃/minute under inert atmosphere and stirring of Zinic stearas and 80～100 times of molar weights is warming up to 260～280 ℃; Splash into the hydrogen peroxide of 15～20 times of Zinic stearas molar weights with 3～6 droplets/second speed, 260～280 ℃ of insulations 2～4 hours; Crude product is purified: crude product is scattered in the toluene, with 3000rpm centrifugal 15 minutes, toluene by volume in the clear liquid that obtains: ethanol=1: 5 adds ethanol, with 3000rpm centrifugal 15 minutes, the precipitation that obtains is disperseed with 2mL toluene, add 10mL ethanol then, centrifugal, the precipitation that obtains centrifugal again 3 times according to the methylbenzene methanol consumption of back; At last the throw out that obtains is dispersed in the toluene, promptly obtains the polycrystalline Nano zinc oxide of plum blossom shape structure.
2, the plum-blossom-like multicrystal-state nano zinc-oxide purticles of claim 1 method preparation, be characterised in that its essentially consist unit is a plum blossom shape polycrystalline Nano zinc oxide, its petal edge is 12～15 nanometers to petal width between centers, the diameter of plum-blossom-like multicrystal-state nano zinc-oxide purticles is in 30 ± 5 nanometers, and petal is evenly distributed.
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| CN101391801B (en) * | 2008-11-06 | 2010-06-02 | 哈尔滨工程大学 | Rose-shaped nano zinc oxide preparation method |
| CN103864137B (en) * | 2014-03-18 | 2015-09-02 | 济南大学 | Flower shape zinc oxide nano material and preparation method thereof |
| CN115924958A (en) * | 2022-11-15 | 2023-04-07 | 华北水利水电大学 | Dispersible zinc oxide or zinc sulfide nano-particles for lubricating grease and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1613774A (en) * | 2004-11-16 | 2005-05-11 | 浙江大学 | Preparation for zinc oxide nanometer material |
| US20060222586A1 (en) * | 2005-03-29 | 2006-10-05 | Headway Advanced Materials Co., Ltd | Preparation method for nanometer grade zinc oxide crystalline (zincite) sol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1613774A (en) * | 2004-11-16 | 2005-05-11 | 浙江大学 | Preparation for zinc oxide nanometer material |
| US20060222586A1 (en) * | 2005-03-29 | 2006-10-05 | Headway Advanced Materials Co., Ltd | Preparation method for nanometer grade zinc oxide crystalline (zincite) sol |
Non-Patent Citations (2)
| Title |
|---|
| Side Reactions in Controlling the Quality, Yield, and Stabilityof High Quality Colloidal Nanocrystals. Yongfen Chen, et al.J. Am. Chem. Soc.,Vol.127 . 2005 * |
| Synthesis of ZnO Nanocrystals with Cone, Hexagonal Cone,and Rod Shapes via Non-Hydrolytic Ester Elimination Sol-GelReactions. Jin Joo, et al.Adv. Mater.,Vol.17 . 2005 * |
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