CN105016314A - Preparation method for zinc selenide nano hollow spheres - Google Patents
Preparation method for zinc selenide nano hollow spheres Download PDFInfo
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- CN105016314A CN105016314A CN201510061202.1A CN201510061202A CN105016314A CN 105016314 A CN105016314 A CN 105016314A CN 201510061202 A CN201510061202 A CN 201510061202A CN 105016314 A CN105016314 A CN 105016314A
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Abstract
The invention discloses a preparation method for zinc selenide nano hollow spheres. The preparation method comprises the following steps: (1) removing an oxide layer on the surface of a target, carrying out ultrasonic cleaning and sucking a liquid on the surface of the target dry by using filter paper; (2) putting the target treated in the step (1) in an opened container in an argon atmosphere, adding chromatographically pure ethanol to submerge the upper surface of the target, adding oleic acid, and ablating the target by using nanosecond parallel pulse laser to obtain a mixed liquid containing zinc nano-particles and taking out the mixed solution from the container; (3) taking and putting oleylamine in another container, injecting the oleylamine into the mixed solution obtained in the step (2) in the argon atmosphere, and heating the solution; and (4) dissolving selenium solution in a mixed solvent at normal temperature, stirring the mixture, injecting the mixture into the mixed solution obtained in the step (3), and heating and insulating the mixture; and centrifugalizing and cleaning the mixture to obtain the zinc selenide nano hollow spheres. The method disclosed by the invention is simple, convenient to operate and easy to control; the zinc selenide nano hollow spheres are synthesized at normal pressure, and the raw materials are non-toxic, so that the preparation method is an environmental-friendly green synthetic method. The produced product is relatively good in crystallinity.
Description
Technical field
The present invention relates to the preparation method of zinc selenide (ZnSe) nano-hollow ball.
Background technology
Zinc selenide (ZnSe) has transmission wave band (0.6 ~ 20um) wider from visible ray to LONG WAVE INFRARED, and uptake factor is very low by (10
-4cm
-1@10um), specific refractory power is very little with the change of wavelength, not easily deliquescence, become the important materials manufacturing the infrared optical elements such as infrared window piece, lens, prism, spectral filter, generally use in the various optical systems such as space remote sensing system, infrared night vision, and there is good thermal shock resistance, therefore become high power CO
2the preferred material of optical element in Optical Maser System, is widely used in high power red outer laser optics.
In addition nearly ten years, hollow Nano particle, because of the performance of its excellence and wide application prospect, becomes the study hotspot of field of nanometer technology gradually.Hollow Nano particle wall thickness is nano level, and internal space proportion is very large, has the characteristics such as density is low, specific surface area is high, thermal expansivity is low, specific refractory power is low, see: X.W.Lou, A.Archer, and Z.Yang, AdvancedMaterials, 2008,20,3987-4019.Therefore, hollow Nano particle to control and environmental safety detects, the field such as biomedical has a good application prospect in the controllable release of high performance lithium ion battery, gas sensor, cell angiographic diagnosis, medicine/gene, catalyzer and support of the catalyst equal energy source, industrial production.According to the Forming Mechanism of hollow structure, the preparation method of hollow Nano particle can be divided into several lower four classes: Ke Kendaer (Kirkendall) effect, chemical etching method, Jia Er Giovanni (galvanic) reduction method, template.Wherein, Kinkendal Effect is a kind of synthetic method of easy, efficient hollow Nano particle.The people such as such as Yin, Y. adopt the method for Kinkendal Effect to obtain cobaltous selenide hollow Nano particle, see: Yin, Y., etal.Science, 2004.304 (5671): p.711-4;
m. the compound hollow Nano particle of people's various cadmium that adopted Kinkendal Effect method to synthesize is waited, see: Chemistry of Materials, 2011.23 (12): p.3095-3104.
At present, the synthesis of zinc selenide hollow ball adopts template mostly, with SiO
2ball, PS ball or N
2bubbles etc. are template, are reunited at template surface by ZnSe nano, then remove template, obtain hollow ball.Due to the restriction of template size, up to now, the ZnSe hollow ball size prepared is mostly micron/submicron level, rarely have the report of below 100nm nano-hollow ball, and the nano-hollow ball being less than 100nm can avoid the scattering loss of as seen-infrared light better.The people such as Karanikolos adopt Normal micelles method (oil-in-water), the liquid crystal formed with segmented copolymer (PEO-PPO-PEO)/water/p-Xylol ternary system is for masterplate, obtain the ZnSe nano-hollow ball of particle diameter 45nm, but crystallinity is poor, see: Langmuir, 2000.16 (8): p.4049-4051.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of zinc selenide nano-hollow ball is provided.
Technical scheme of the present invention is summarized as follows:
A preparation method for zinc selenide nano-hollow ball, comprises the steps:
(1) with the surface of the block zinc target of sand papering to remove the zone of oxidation of its target material surface, then be placed in chromatographically pure ethanol ultrasonic cleaning 1-3min; Clean 2-4 time, blot target material surface liquid with filter paper;
(2) target after step (1) being processed puts into the open container under argon atmospher, add chromatographically pure ethanol and make not have target upper surface, add the oleic acid being equivalent to chromatographically pure ethanol contend 0.01%-0.02%, employing wavelength is the nanosecond parallel pulse laser ablation target of 1064nm, target is moved every 2-4min, ablation 5-60min altogether, obtains the mixing liquid containing zinc nanoparticles and takes out from container;
(3) get oleyl amine and put into another container, under an argon, the mixing liquid that implantation step (2) obtains, is heated to 230 DEG C-260 DEG C, and the volume ratio of the chromatographically pure ethanol of described oleyl amine and step (2) is 1:1-3;
(4) at normal temperatures, selenium powder is dissolved in the mixed solvent of oleyl amine that volume ratio is 1:1 and Dodecyl Mercaptan composition, the mol ratio of selenium powder and Dodecyl Mercaptan is 1:1-2, in the mixing solutions that after stirring 1-10min, implantation step (3) obtains, Heating temperature is to 230 DEG C-260 DEG C and soaking time is 1-90 minute; Centrifugal, and be that the ethanol of 1:1 and the mixing solutions of normal hexane clean 2-5 time by normal hexane or volume ratio, obtain zinc selenide nano-hollow ball, be dispersed in normal hexane, the mol ratio of described selenium powder and zinc nanoparticles is more than or equal to 1.
The purity of block zinc target is 99.99%.The thickness of block zinc target can be the thickness of any appropriate, is advisable with 3-7mm.
In step (2), the distance of the liquid level distance target upper surface of chromatographically pure ethanol is preferably 3-7mm.
Nanosecond parallel pulse laser the preferred 170-250mJ of energy, the preferred 5-10HZ of laser repetition rate.
The centrifugal revolution of step (4) selects 8000-20000rpm preferably, and the centrifugal time is 10-30min.
Step (4) described temperature preferably 260 DEG C, soaking time preferably 1 minute.
Instant invention overcomes the problem that existing synthetic method fails to obtain zinc selenide nano-hollow ball (ZnSe HNPs).Demonstrate ZnSe HNPs first to be generated by Kinkendal Effect.Synthetic method craft of the present invention is simple, easy to operate, be easy to control, and belonging to normal pressure synthesis, do not use poisonous reaction raw materials, is a kind of eco-friendly green synthesis method.The crystallinity of the product produced is better.
Accompanying drawing explanation
Fig. 1 is the sign of zinc nanoparticles, and wherein (a) is Zn nano particle low power transmission electron microscope photo; B high resolution transmission electron microscopy photo that () is Zn nano particle; C selected area electron diffraction that () is Zn nano particle is composed; D () is Zn nano particle energy spectrum analysis figure.
The sign of Fig. 2 zinc selenide nano-hollow ball ZnSe HNPs, wherein (a) is ZnSe HNPs low power transmission electron microscope photo; (b) ZnSe HNPs energy spectrum analysis figure; C () is ZnSe HNPs high resolution transmission electron microscopy photo; D XRD analysis figure that () is Zn nano particle and ZnSe HNPs.
Fig. 3 is the hollow process of ZnSe HNPs.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
A preparation method for zinc selenide nano-hollow ball, comprises the steps:
(1) with the surface of the block zinc target of sand papering to remove the zone of oxidation of its target material surface, then be placed in chromatographically pure ethanol ultrasonic cleaning 2min; Clean 3 times, blot target material surface liquid with filter paper; The purity of block zinc target is 99.99%.The thickness of block zinc target is 5mm.
(2) target after step (1) being processed puts into the open container under argon atmospher, add chromatographically pure ethanol and make not have target upper surface, add the oleic acid being equivalent to chromatographically pure ethanol contend 0.01%, employing wavelength is the nanosecond parallel pulse laser ablation target of 1064nm, target is moved every 3min, ablation 30min altogether, obtains the mixing liquid containing zinc nanoparticles and takes out from container; The distance of the liquid level distance target upper surface of chromatographically pure ethanol is 5mm; Laser energy is 200mJ laser repetition rate is 10HZ.(sign of zinc nanoparticles is shown in Fig. 1)
(3) get oleyl amine and put into another container, under an argon, the mixing liquid that implantation step (2) obtains, is heated to 245 DEG C, and the volume ratio of the chromatographically pure ethanol of described oleyl amine and step (2) is 1:2;
(4) at normal temperatures, selenium powder is dissolved in the mixed solvent of oleyl amine that volume ratio is 1:1 and Dodecyl Mercaptan composition, the mol ratio of selenium powder and Dodecyl Mercaptan is 1:1, in the mixing solutions that after stirring 5min, implantation step (3) obtains, Heating temperature is to 260 DEG C and soaking time is 1 minute; At the centrifugal 15min of 10000rpm, and be that the ethanol of 1:1 and the mixing solutions of normal hexane clean 3 times by volume ratio, obtain zinc selenide nano-hollow ball, be dispersed in normal hexane (see Fig. 2, can find out that from Fig. 2 (c) crystallinity of zinc selenide nano-hollow ball is better), the mol ratio of described selenium powder and zinc nanoparticles equals 1.5.
Embodiment 2
A preparation method for zinc selenide nano-hollow ball, comprises the steps:
(1) with the surface of the block zinc target of sand papering to remove the zone of oxidation of its target material surface, then be placed in chromatographically pure ethanol ultrasonic cleaning 1min; Clean 4 times, blot target material surface liquid with filter paper; The purity of block zinc target is 99.99%.The thickness of block zinc target is 3mm.
(2) target after step (1) being processed puts into the open container under argon atmospher, add chromatographically pure ethanol and make not have target upper surface, add the oleic acid being equivalent to chromatographically pure ethanol contend 0.02%, employing wavelength is the nanosecond parallel pulse laser ablation target of 1064nm, target is moved every 4min, ablation 60min altogether, obtains the mixing liquid containing zinc nanoparticles and takes out from container; The distance of the liquid level distance target upper surface of chromatographically pure ethanol is 3mm; Laser energy is 170mJ, and laser repetition rate is 10HZ.
(3) get oleyl amine and put into another container, under an argon, the mixing liquid that implantation step (2) obtains, is heated to 230 DEG C DEG C, and the volume ratio of the chromatographically pure ethanol of described oleyl amine and step (2) is 1:1;
(4) at normal temperatures, selenium powder is dissolved in the mixed solvent of oleyl amine that volume ratio is 1:1 and Dodecyl Mercaptan composition, the mol ratio of selenium powder and Dodecyl Mercaptan is 1:1, in the mixing solutions that after stirring 1min, implantation step (3) obtains, Heating temperature is to 230 DEG C and soaking time is 10 minutes; At the centrifugal 30min of 8000rpm, and be that the ethanol of 1:1 and the mixing solutions of normal hexane clean 2 times by volume ratio, obtain zinc selenide nano-hollow ball, be dispersed in normal hexane, the mol ratio of described selenium powder and zinc nanoparticles equals 1.
Experiment proves, the method for the present embodiment obtains the good zinc selenide nano-hollow ball of crystallinity.
Embodiment 3
A preparation method for zinc selenide nano-hollow ball, comprises the steps:
(1) with the surface of the block zinc target of sand papering to remove the zone of oxidation of its target material surface, then be placed in chromatographically pure ethanol ultrasonic cleaning 3min; Clean 2 times, blot target material surface liquid with filter paper; The purity of block zinc target is 99.99%.The thickness of block zinc target is 7mm.
(2) target after step (1) being processed puts into the open container under argon atmospher, add chromatographically pure ethanol and make not have target upper surface, add the oleic acid being equivalent to chromatographically pure ethanol contend 0.01%, employing wavelength is the nanosecond parallel pulse laser ablation target of 1064nm, target is moved every 2min, ablation 5min altogether, obtains the mixing liquid containing zinc nanoparticles and takes out from container; The distance of the liquid level distance target upper surface of chromatographically pure ethanol is 7mm; Laser energy is 250mJ, and laser repetition rate is 5HZ.
(3) get oleyl amine and put into another container, under an argon, the mixing liquid that implantation step (2) obtains, is heated to 260 DEG C, and the volume ratio of the chromatographically pure ethanol of described oleyl amine and step (2) is 1:3;
(4) at normal temperatures, selenium powder is dissolved in the mixed solvent of oleyl amine that volume ratio is 1:1 and Dodecyl Mercaptan composition, the mol ratio of selenium powder and Dodecyl Mercaptan is 1:2, in the mixing solutions that after stirring 10min, implantation step (3) obtains, Heating temperature is to 260 DEG C and soaking time is 90 minutes; At the centrifugal 10min of 20000rpm, and clean 5 times with the mixing solutions of normal hexane, obtain zinc selenide nano-hollow ball, be dispersed in normal hexane, the mol ratio of described selenium powder and zinc nanoparticles equals 2.
What step (2) obtained adopts atomic absorption method to measure containing the concentration of zinc nanoparticles in the mixing liquid of zinc nanoparticles, also empirically can judge according to the color of mixing liquid.
Experiment proves, the method for the present embodiment obtains the good zinc selenide nano-hollow ball of crystallinity.
Fig. 3 is that method of the present invention makes the hollow forming process of ZnSe HNPs by Kinkendal Effect.
Claims (5)
1. a preparation method for zinc selenide nano-hollow ball, is characterized in that comprising the steps:
(1) with the surface of the block zinc target of sand papering to remove the zone of oxidation of its target material surface, then be placed in the ultrasonic cleaning of chromatographically pure ethanol, blot target material surface liquid with filter paper;
(2) target after step (1) being processed puts into the open container under argon atmospher, add chromatographically pure ethanol and make not have target upper surface, add the oleic acid being equivalent to chromatographically pure ethanol contend 0.01%-0.02%, employing wavelength is the nanosecond parallel pulse laser ablation target of 1064nm, target is moved every 2-4min, ablation 5-60min altogether, obtains the mixing liquid containing zinc nanoparticles and takes out from container.
(3) get oleyl amine and put into another container, under an argon, the mixing liquid that implantation step (2) obtains, is heated to 230 DEG C-260 DEG C, and the volume ratio of the chromatographically pure ethanol of described oleyl amine and step (2) is 1:1-3;
(4) at normal temperatures, selenium powder is dissolved in the mixed solvent of oleyl amine that volume ratio is 1:1 and Dodecyl Mercaptan composition, the mol ratio of selenium powder and Dodecyl Mercaptan is 1:1-2, in the mixing solutions that after stirring 1-10min, implantation step (3) obtains, Heating temperature is to 230 DEG C-260 DEG C and soaking time is 1-90 minute; Centrifugal, and be the ethanol of 1:1 and the mixing solutions cleaning of normal hexane by normal hexane or volume ratio, obtain zinc selenide nano-hollow ball, be dispersed in normal hexane, the mol ratio of described selenium powder and zinc nanoparticles is more than or equal to 1.
2. the preparation method of a kind of zinc selenide nano-hollow ball according to claim 1, is characterized in that the purity of described block zinc target is 99.99%.
3. the preparation method of a kind of zinc selenide nano-hollow ball according to claim 1, is characterized in that the liquid level of chromatographically pure ethanol in described step (2) is 3-7mm apart from the distance of target upper surface.
4. the preparation method of a kind of zinc selenide nano-hollow ball according to claim 1, it is characterized in that the energy of parallel pulse laser of described nanosecond is 170-250mJ, laser repetition rate is 5-10HZ.
5. a kind of preparation method preparing zinc selenide nano-hollow ball according to claim 1, it is characterized in that step (4) described temperature is 260 DEG C, described soaking time is 1 minute.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110240125A (en) * | 2018-03-08 | 2019-09-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of hollow selenizing zinc nanocrystalline, preparation method and application |
| CN114632481A (en) * | 2022-03-04 | 2022-06-17 | 安徽大学 | Method for preparing uniformly dispersed metal nanoparticle colloid |
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| CN110133764B (en) * | 2018-02-08 | 2020-08-21 | 天津大学 | Preparation method of zinc selenide nano hollow sphere double-layer graded-refractive-index antireflection film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920942A (en) * | 2010-09-20 | 2010-12-22 | 东华大学 | Method for controlling synthesis of zinc selenide multi-morphological nano material |
| CN102659083A (en) * | 2012-04-27 | 2012-09-12 | 吉林大学 | Hollow copper telluride nanometer crystal and preparation method and application thereof |
| CN102874773A (en) * | 2012-09-10 | 2013-01-16 | 江苏大学 | Preparation method of porous nickel selenide hollow nanospheres |
-
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- 2015-02-05 CN CN201510061202.1A patent/CN105016314B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920942A (en) * | 2010-09-20 | 2010-12-22 | 东华大学 | Method for controlling synthesis of zinc selenide multi-morphological nano material |
| CN102659083A (en) * | 2012-04-27 | 2012-09-12 | 吉林大学 | Hollow copper telluride nanometer crystal and preparation method and application thereof |
| CN102874773A (en) * | 2012-09-10 | 2013-01-16 | 江苏大学 | Preparation method of porous nickel selenide hollow nanospheres |
Non-Patent Citations (2)
| Title |
|---|
| SRAVANI GULLAPALLI ET AL.: "Molten-droplet synthesis of composite CdSe hollow nanoparticles", 《NANOTECHNOLOGY》 * |
| YADONG YIN ET AL.: "Formation of Hollow Nanocrystals Through the Nanoscale Kirkendall Effect", 《SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240125A (en) * | 2018-03-08 | 2019-09-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of hollow selenizing zinc nanocrystalline, preparation method and application |
| CN110240125B (en) * | 2018-03-08 | 2021-03-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Hollow zinc selenide nanocrystal and preparation method and application thereof |
| CN114632481A (en) * | 2022-03-04 | 2022-06-17 | 安徽大学 | Method for preparing uniformly dispersed metal nanoparticle colloid |
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Address after: 300350 District, Jinnan District, Tianjin Haihe Education Park, 135 beautiful road, Beiyang campus of Tianjin University Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92 Patentee before: Tianjin University |