CN103725287A - Composite nanocrystalline material ZnSe/ZnS/MnS with core-shell structure and preparation method thereof - Google Patents
Composite nanocrystalline material ZnSe/ZnS/MnS with core-shell structure and preparation method thereof Download PDFInfo
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- CN103725287A CN103725287A CN201310754589.XA CN201310754589A CN103725287A CN 103725287 A CN103725287 A CN 103725287A CN 201310754589 A CN201310754589 A CN 201310754589A CN 103725287 A CN103725287 A CN 103725287A
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Abstract
The invention discloses a composite nanocrystalline material ZnSe/ZnS/MnS with a core-shell structure and a preparation method thereof. The composite nanocrystalline material ZnSe/ZnS/MnS with the core-shell structure consists of a core layer, an intermediate layer and a shell layer, wherein the core layer is ZnSe, the intermediate layer is ZnS and the shell layer is MnS; and mol ratio of ZnSe to ZnS to MnS is at 2:10:1. Photoluminescence spectrum of the ZnSe/ZnS/MnS composite nanocrystalline material is continuously distributed in a visible light range, and has three main luminescence peaks, thus representing white light. The non-toxic and white-light ZnSe/ZnS/MnS composite nanocrystalline material prepared by the invention is good in water solubility and stable in structure, and has a certain application prospect in the fields such as biological detector, display component and the like.
Description
One, technical field
The present invention relates to a kind of nanocrystalline material and preparation method thereof, specifically a kind of composite nanocrystalline material ZnSe/ZnS/MnS with nucleocapsid structure and preparation method thereof, is a kind of nanocrystalline material of water phase non-toxic white light nucleocapsid structure.
Two, background technology
Size is called nano material at the material of nanoscale structures.Nano material is because quantum effect and surface effects have had the character such as unique optics, electricity, machinery, chemistry.II-VI family nanocrystalline material has the luminous character in visible region, therefore at aspects such as fluorescent mark, photosensor and luminescent devices, has broad application prospects.In application process, not only require pure, the stable and monodispersity of nanocrystalline material, and need nontoxicity and water-soluble.Cadmium class is nanocrystalline has limited its range of application owing to having toxicity.The congeners of cadmium, zinc class nanocrystalline material more and more receives people's concern as zinc telluridse, zinc selenide, zinc sulphide and zinc oxide etc.
In the research field of nanocrystalline material, an important aspect is using the particle of nanostructure as " building block (building block, constructional unit) ", to carry out construction structure complexity and orderly advanced composite material.Along with the development of nano material technology, requirement is also day by day complicated as the Nomenclature Composition and Structure of Complexes of the nanocrystalline particle of " building block ", so people have produced dense research interest to the composite nanocrystalline particle of nucleocapsid structure.The composite nanocrystalline particle of nucleocapsid structure is comprised of at least two kinds of different materials, and wherein a kind of material forms core, and other material forms outer shell.The composite particles of this nucleocapsid structure can design and cutting on nanoscale, thereby has physics and the chemical property such as unique optical, electrical, magnetic, catalysis of the nanocrystalline particle that is different from single component.
Realize the white luminous several different methods that has, as the material mixing of blue light-emitting, green glow and ruddiness, or by the material mixing of blue light-emitting and gold-tinted.The preparation of the brilliant material of white-light nanometer is at present to mix generation with the cadmium class nanocrystalline material of blue light-emitting, ruddiness and green glow substantially.The preparation of the brilliant material of single water phase non-toxic white-light nanometer can better expand the range of application of nanocrystalline material.
Three, summary of the invention
The present invention aims to provide a kind of composite nanocrystalline material ZnSe/ZnS/MnS with nucleocapsid structure and preparation method thereof, and composite nanocrystalline material of the present invention emits white light, and has water-soluble and stability preferably, nontoxic.
The present invention has the composite nanocrystalline material ZnSe/ZnS/MnS of nucleocapsid structure, is to consist of stratum nucleare, middle layer and shell, and described stratum nucleare is ZnSe, and described middle layer is ZnS, and described shell is MnS, and the mol ratio of ZnSe, ZnS and MnS is 2:10:1.
The preparation method that the present invention has the composite nanocrystalline material ZnSe/ZnS/MnS of nucleocapsid structure operates according to the following steps:
1) the nanocrystalline preparation of ZnSe
Zinc nitrate and thiohydracrylic acid (MPA) are added to the water, with adding sodium hydrogen selenide after nitrogen deoxygenation, at 100 ℃, after back flow reaction 2-6 hour, obtain ZnSe nanocrystal solution, the mol ratio of zinc nitrate, thiohydracrylic acid and sodium hydrogen selenide is 1:2:0.2; Reflux time is preferably 2 hours.
2) preparation of ZnSe/ZnS composite nanocrystalline
In freshly prepd ZnSe nanocrystal solution, add zinc nitrate solution, thioacetyl amine aqueous solution and thiohydracrylic acid, adjust pH is 11-12, and at 100 ℃, back flow reaction is 10 minutes, obtains ZnSe/ZnS nanocrystal solution; Wherein the mol ratio of nanocrystalline, the zinc nitrate of ZnSe, thioacetamide and thiohydracrylic acid is 1:5:10:5, and the nanocrystalline molar weight of ZnSe is in the molar weight of nanocrystalline middle Se atom.
3) preparation of ZnSe/ZnS/MnS composite nanocrystalline
To step 2) add manganese nitrate solution, thioacetyl amine aqueous solution and thiohydracrylic acid in the ZnSe/ZnS nanocrystal solution prepared, adjust pH is 11-12, at 100 ℃, back flow reaction obtains ZnSe/ZnS/MnS composite nanocrystalline after 20 minutes; Wherein the mol ratio of nanocrystalline, the manganous nitrate of ZnSe/ZnS, thioacetamide and thiohydracrylic acid is 2:1:2:10, and the nanocrystalline molar weight of ZnSe/ZnS is in the molar weight of nanocrystalline middle Se atom.
The sodium hydrogen selenide that the present invention uses prepares by sodium borohydride reduction selenium powder, and reaction process is as follows:
0.51g sodium borohydride and 0.48g selenium powder are put into reaction vessel, reaction vessel is sealed with plug after adding rapidly 9mL deionized water, on plug, insert a little pin hole and communicate so that the hydrogen producing in release reaction process with the external world.For preventing that the too violent consequently selenium powder of reaction process from stopping up pin hole, in reaction process, to put into ice-water bath cooling for system, react the selenium powder of black after 7.5-8.5 hour and disappear and produce white Sodium Tetraborate crystal, upper strata is clarified water white solution and is sodium hydrogen selenide solution, and concentration is 0.667mol/L.
Composite nanocrystalline material of the present invention, not have virose zinc element to substitute poisonous cadmium element, has been realized nanocrystalline nontoxicity.The photoluminescence spectra of composite nanocrystalline material of the present invention distributes continuously in visible-range, has three main glow peaks to lay respectively at 398nm, near 487nm and 562nm, presents white luminous.ZnSe/ZnS/MnS composite nanocrystalline of the present invention is spherical in shape, and diameter is 6nm left and right, presents obvious crystalline network.
Compared with prior art, tool of the present invention has the following advantages:
1, the present invention has prepared the ZnSe/ZnS/MnS composite nanocrystalline of nucleocapsid structure by involucrum, has obtained the nanocrystalline material of transmitting white, has realized the photic white light of independent nanocrystalline material.
2, the present invention is not to have virose zinc element to substitute poisonous cadmium element, and synthetic white-light nanometer material does not have toxicity, can better be applied to the fields such as biological detection, display device.
3, ZnSe/ZnS/MnS composite nanocrystalline of the present invention is directly synthetic in the aqueous solution, therefore has water-soluble preferably.In addition, to newly synthesize the lucifuge placement at normal temperatures of ZnSe/ZnS/MnS composite nanocrystalline solution after 3 months, the luminescent spectrum feature of its luminescent spectrum and freshly prepd sample is basic identical, illustrate that the phenomenons such as decomposition or aggregate and precipitate occur the ZnSe/ZnS/MnS composite nanocrystalline material that this method obtains in put procedure, have good stability.
4, composite nanocrystalline material of the present invention to prepare required equipment simple, the used time is short, easily operation, favorable repeatability, cheap and not dangerous.
5, composite nanocrystalline material of the present invention photoluminescence spectra under the exciting of UV-light is continuous, and spectrum peak is level and smooth, approaches solar spectrum.
Four, accompanying drawing explanation
Fig. 1 is the photoluminescence spectra of ZnSe/ZnS/MnS composite nanocrystalline material of the present invention.Sample (a) and (b) and (c) be respectively reflux 2.5,4 and 6 hours in the nanocrystalline preparation process of ZnSe.Excitation wavelength is 350nm.The photoluminescence spectra of ZnSe/ZnS/MnS composite nanocrystalline distributes continuously in visible-range, has three main glow peaks to lay respectively at 398nm, 487nm and 562nm.Wherein 398nm is the band-edge luminescence peaks of ZnSe, and 487nm is the defect luminescence peak of ZnSe, and the glow peak at 562nm place is the glow peak of outer shell Mn/S.
Fig. 2 is the high resolution transmission electron microscopy picture of ZnSe/ZnS/MnS composite nanocrystalline of the present invention (a) and ZnSe/ZnS nanocrystalline (b).White light ZnSe/ZnS/MnS prepared by the present invention is nanocrystalline spherical in shape, presents obvious crystalline network.
Fig. 3 be ZnSe/ZnS/MnS composite nanocrystalline material of the present invention X ray diffracting spectrum and with the contrast of ZnSe and the ZnS of body phase.Crystal formation that ZnSe/ZnS/MnS is nanocrystalline and the formation of nucleocapsid structure have been described.
Five, embodiment
The present invention's raw material zinc nitrate, thiohydracrylic acid, sodium borohydride, selenium powder, thioacetamide, manganous nitrate, sodium hydroxide used is analytical reagent, and solvent is high-purity deionized water.
1, the preparation of sodium hydrogen selenide solution:
Sodium hydrogen selenide solution is prepared by sodium borohydride reduction selenium powder, and reaction equation is as follows:
Concrete operations are:
0.51g sodium borohydride and 0.48g selenium powder are put into reaction vessel, reaction vessel is sealed with plug after adding rapidly 9mL deionized water, on plug, insert a little pin hole and communicate so that the hydrogen producing in release reaction process with the external world.For preventing that the too violent so that selenium powder of reaction process from stopping up pin hole, in reaction process, to put into ice-water bath cooling for system, reacts the selenium powder of black after 7.5-8.5 hour and disappear and produce white Sodium Tetraborate crystal.It is sodium hydrogen selenide that water white solution is clarified on upper strata, and concentration is 0.667mol/L.
2, the nanocrystalline preparation of ZnSe:
The zinc nitrate solution that is 0.1mol/L by 20mL concentration joins in the three-necked bottle that 200 ml deionized water are housed; then add 0.346mL thiohydracrylic acid; sodium hydroxide solution adjust pH to 9.3 with 1mol/L; be uniformly mixed; under nitrogen protection to the sodium hydrogen selenide solution 0.6mL that adds step 1 preparation in three-necked bottle; in nitrogen atmosphere, in 100 ℃ of heating reflux reactions, after 2 hours, obtain ZnSe nanocrystal solution, wherein mol ratio Zn/MPA/Se=1:2:0.2.
3, the preparation of ZnSe/ZnS/MnS composite nanocrystalline:
The thioacetyl amine aqueous solution that the zinc nitrate solution that is 0.1mol/L by 20mL concentration and 20mL concentration are 0.1mol/L mixes, and then adds 0.346mL thiohydracrylic acid, and adjust pH is 11.4; Above-mentioned solution is joined in the ZnSe nanocrystal solution of step 2 preparation, at 100 ℃, heating reflux reaction is 10 minutes, obtain ZnSe/ZnS nanocrystal solution, adding subsequently 2mL concentration is the thiohydracrylic acid of 0.1mol/L manganous nitrate and 35 microlitres, adjusting pH is 11.4, adding 20mL concentration is the thioacetyl amine aqueous solution of 0.1mol/L again, continues back flow reaction and after 20 minutes, obtains ZnSe/ZnS/MnS nucleocapsid structure composite nanocrystalline.Add manganese atom in material, thiohydracrylic acid and sulphur atom mol ratio be Mn/MPA/S=1/2/10.
Claims (3)
1. a composite nanocrystalline material ZnSe/ZnS/MnS with nucleocapsid structure, it is characterized in that: described composite nanocrystalline material consists of stratum nucleare, middle layer and shell, described stratum nucleare is ZnSe, and described middle layer is ZnS, described shell is MnS, and the mol ratio of ZnSe, ZnS and MnS is 2:10:1.
2. a preparation method with the composite nanocrystalline material ZnSe/ZnS/MnS of nucleocapsid structure claimed in claim 1, is characterized in that operating according to the following steps:
1) the nanocrystalline preparation of ZnSe
Zinc nitrate and thiohydracrylic acid are added to the water, with adding sodium hydrogen selenide after nitrogen deoxygenation, at 100 ℃, after back flow reaction 2-6 hour, obtain ZnSe nanocrystal solution, the mol ratio of zinc nitrate, thiohydracrylic acid and sodium hydrogen selenide is 1:2:0.2;
2) preparation of ZnSe/ZnS composite nanocrystalline
In freshly prepd ZnSe nanocrystal solution, add zinc nitrate solution, thioacetyl amine aqueous solution and thiohydracrylic acid, adjust pH is 11-12, and at 100 ℃, back flow reaction is 10 minutes, obtains ZnSe/ZnS nanocrystal solution; Wherein the mol ratio of nanocrystalline, the zinc nitrate of ZnSe, thioacetamide and thiohydracrylic acid is 1:5:10:5;
3) preparation of ZnSe/ZnS/MnS composite nanocrystalline
To step 2) add manganese nitrate solution, thioacetyl amine aqueous solution and thiohydracrylic acid in the ZnSe/ZnS nanocrystal solution prepared, adjust pH is 11-12, at 100 ℃, back flow reaction obtains ZnSe/ZnS/MnS composite nanocrystalline after 20 minutes; Wherein the mol ratio of nanocrystalline, the manganous nitrate of ZnSe/ZnS, thioacetamide and thiohydracrylic acid is 2:1:2:10.
3. preparation method according to claim 1, is characterized in that:
In step 1), reflux time is 2 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602508A (en) * | 2022-04-02 | 2022-06-10 | 吉林化工学院 | Preparation and application of MnS @ ZnS core-shell hollow sphere with photocatalytic performance |
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Non-Patent Citations (2)
| Title |
|---|
| XU,S.等: "SYNTHESIS OF NONTOXIC WHITE LIGHT ZNSE/ZNS/MNS QUANTUM DOTS", 《LIGHTING QUALITY & ENERGY EFFICIENCY 》 * |
| 陈秀秀 等: "ZnSe /ZnS核壳结构量子点的制备与表征", 《人工晶体学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602508A (en) * | 2022-04-02 | 2022-06-10 | 吉林化工学院 | Preparation and application of MnS @ ZnS core-shell hollow sphere with photocatalytic performance |
| CN114602508B (en) * | 2022-04-02 | 2023-08-04 | 吉林化工学院 | Preparation and application of MnS@ZnS core-shell hollow sphere catalyst with photocatalytic performance |
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Application publication date: 20140416 |