CN101734616A - Method for preparing silicon dioxide hybridized quantum dot by using one-pot method - Google Patents
Method for preparing silicon dioxide hybridized quantum dot by using one-pot method Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 112
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 22
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 11
- 238000005580 one pot reaction Methods 0.000 title abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 210000001124 body fluid Anatomy 0.000 claims description 18
- 239000010839 body fluid Substances 0.000 claims description 18
- -1 sulfhydryl compound Chemical class 0.000 claims description 17
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 12
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 claims description 8
- 229910000059 tellane Inorganic materials 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 239000011669 selenium Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- PBFKVYVGYHNCGT-UHFFFAOYSA-N 1-sulfanylpropane-1,2,3-triol Chemical compound OCC(O)C(O)S PBFKVYVGYHNCGT-UHFFFAOYSA-N 0.000 claims description 5
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229940075417 cadmium iodide Drugs 0.000 claims description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 3
- PSIBWKDABMPMJN-UHFFFAOYSA-L cadmium(2+);diperchlorate Chemical compound [Cd+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PSIBWKDABMPMJN-UHFFFAOYSA-L 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- VTLHPSMQDDEFRU-UHFFFAOYSA-N tellane Chemical compound [TeH2] VTLHPSMQDDEFRU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- 108010024636 Glutathione Proteins 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229940117941 cadmium sulfate Drugs 0.000 claims description 2
- KTTSJTVLWUJJMN-UHFFFAOYSA-L cadmium(2+);dichlorate Chemical compound [Cd+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O KTTSJTVLWUJJMN-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 229960003180 glutathione Drugs 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229940102001 zinc bromide Drugs 0.000 claims description 2
- GTQFPPIXGLYKCZ-UHFFFAOYSA-L zinc chlorate Chemical compound [Zn+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O GTQFPPIXGLYKCZ-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000000090 biomarker Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 3
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 29
- 229910004613 CdTe Inorganic materials 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 7
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
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- 238000002189 fluorescence spectrum Methods 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing silicon dioxide hybridized quantum dot by using a one-pot method. The invention comprises the following steps of: adding a non-metal ion source needed for preparing quantum dots to a quantum dot metal ion source containing mercapto stabilizer in a water phase system, getting the precursor liquid of quantum dot under the protection of a nitrogen atmosphere, then adding the silicon dioxide to the precursor liquid of quantum dot and reacting the silicon dioxide with the precursor liquid of quantum dot to obtain the silicon dioxide hybridized quantum dot. The silicon dioxide hybridized quantum dot obtained in the invention has the advantages of good dissolubility, excellent luminous performance and optical stability, good biocompatibility and biological stability, and good prospect of application in the aspects of biomarker and function materials.
Description
Technical field
That the present invention relates to is the preparation method of field of nanometer technology, specifically is a kind of method of method for preparing silicon dioxide hybridized quantum dot by using one-pot,
Background technology
The wavelength of fluorescence of quantum dot or glow color can be regulated by particle diameter at an easy rate, the luminous quantum efficiency height, have narrow and symmetrical emission spectrum and wide and continuous absorption spectrum, these characteristics make quantum dot demonstrate wide application prospect in fields such as biomarker, luminescent device, composite, solar cells.However, synthetic quantum dot also has some important disadvantages such as luminous to stablize, be difficult to a large amount of preparations, toxicity inadequately big etc., thereby makes quantum dot be difficult to be used widely.In order to solve these shortcomings, can coat layer of silicon dioxide on the surface of quantum dot.Silica has good optical and chemical stability, both can protect quantum dot can also do not improved the anti-environment capacity of quantum dot by photooxidation.Simultaneously, the good biocompatibility of silica can reduce the toxicity of quantum dot greatly, helps its biologic applications.In addition, the raw material of preparation silica is cheap, helps a large amount of preparations.Thereby preparation quantum dot-silica hybrid material is subjected to the extensive concern of academia.People such as Rogach synthesize CdTe, CdSe, CdSe/CdS quantum dot earlier, utilize again sol-gel process with coated with silica on quantum dot, obtain quantum dot (Chem.Mater.2000,12 (9): 2676-2685) of SiO 2 hybrid.People such as Gao at first prepare water miscible CdTe quantum dot, utilize the method for reverse micro emulsion successfully to prepare silica-cadmium telluride hybrid particle (Adv.Mater.2005,17 (19): 2354-2357) then.People such as Ying have reported that quantum efficiency is the preparation of the CdSe quantum dot of 20% SiO 2 hybrid, its synthetic method is to prepare oil-soluble CdSe quantum dot earlier, then its surface is modified and increased hydrophily, utilize the method for reverse micro emulsion to wrap up silica (Adv.Mater.2005,17 (13): 1620-1625) again.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of one kettle way to prepare the method for the quantum dot of SiO 2 hybrid.
The method that one kettle way prepares the quantum dot of SiO 2 hybrid may further comprise the steps:
Step (a): metal ion source and sulfhydryl compound are dissolved in the deionized water, the concentration of metal ion source is every liter of 0.01～300 mM, the mol ratio of sulfydryl sulfhydryl compound and metal ion source is 1～6: 1, adding hydroxide regulator solution pH value is 7～10, makes quantum dot metal ion precursor solution;
Step (b): logical nitrogen and the temperature of solution is raised to 90～100 ℃ in the quantum dot metal ion precursor solution, the nonmetallic ion source aqueous solution is injected this metal ion precursor solution, the mol ratio of nonmetallic ion source and metal ion source is 0.6～1.3: 1, makes the preceding body fluid of quantum dot;
Step (c): silica source is injected in the preceding body fluid of quantum dot, the mol ratio of silica source and metal ion source is 0.5～800: 1, reacts 0.2～108 hour down at 85～100 ℃, makes the quantum dot of SiO 2 hybrid.
Metal ion source described in the step (a) is zinc chloride, caddy, lead chloride, zinc bromide, cadmium iodide, zinc chlorate, cadmium chlorate, zinc perchlorate, cadmium perchlorate, zinc nitrate, cadmium nitrate, plumbi nitras, zinc acetate, cadmium acetate, lead acetate, zinc sulfate or cadmium sulfate.Sulfhydryl compound comprises TGA, mercaptopropionic acid, mercaptoethanol, mercaprol, mercapto glycerol, mercaptoethylmaine, sulfydryl propylamine, sulfydryl butylamine or glutathione described in the step (a).The mol ratio of sulfydryl stabilizing agent and metal ion source is 2～5: 1 described in the step (a).The concentration of quantum dot metal ion source is every liter of 0.01～200 mM in the step (a).Hydroxide comprises NaOH, potassium hydroxide described in the step (a); The pH value of quantum dot metal ion prerequisite solution is 7.5～10.The nonmetal source of the preparation quantum dot described in the step (b) comprises vulcanized sodium, potassium sulfide, sodium hydrogen telluride, hydrogen telluride potassium, sodium hydrogen selenide or selenium hydrofining.The mol ratio of the metal ion source in the step (b) in nonmetallic ion source and the step (a) is 0.7～1.2: 1.Used silica source comprises methyl silicate, ethyl orthosilicate, silicic acid four butyl esters or silicon tetrachloride in the step (c); The mol ratio of the metal ion source in silica source and the step (a) is 1～600: 1.The reaction time is 0.5～72 hour in the step (c).
The optical characteristics of the quantum dot of the SiO 2 hybrid that the present invention obtains is tested with absorption spectrometer and XRF, pattern is analyzed with the transmission electron microscope (TEM) of high power, toxicity adopts the cytotoxicity experiment test, and the quantum dot of SiO 2 hybrid also adopts x-ray diffractometer, x-ray photoelectron power spectrum, infrared spectrum etc. to characterize in addition.
The quantum dot of SiO 2 hybrid prepared in accordance with the present invention has fabulous dissolubility, helps carrying out further modification; Have excellent luminescent properties, and emission wavelength can regulate and control by the kind of reaction time and sulfydryl stabilizing agent, can satisfy different luminous demands; Fluorescent stability is strong, and toxicity is low, suitable biomarker, lighting function material, the solar cell etc. of being applied to; Ultra-fine particle diameter, can be used for doing the additive of polymer composites, be expected to improve when giving the polymerization luminescent properties mechanical property of polymer, in addition, the quantum dot that utilizes the present invention to prepare is also having good prospects for application aspect anti-fake material and the luminous printing ink.
Description of drawings
Fig. 1 utilizes the fluorescence spectrum figure of mercapto glycerol for the CdTe quantum dot of the SiO 2 hybrid of stabilizing agent preparation;
Fig. 2 utilizes the fluorescence spectrum figure of mercaptopropionic acid for the CdTe quantum dot of the SiO 2 hybrid of stabilizing agent preparation;
Fig. 3 is the transmission electron microscope figure of the CdTe quantum dot of SiO 2 hybrid.
The specific embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
With the cadmium acetate is the source metal of preparation quantum dot, the mercaptopropionic acid stabilizing agent, and sodium hydrogen selenide is the nonmetal source of preparation quantum dot, ethyl orthosilicate is a silica source, the CdSe quantum dot of preparation SiO 2 hybrid.
Step (a): in 2 liters reaction bulb, adding 1.33 gram cadmium acetates and 2.55 gram mercaptopropionic acids in 1.5 liters of deionized waters, is 8.0 with sodium hydrate regulator solution pH value, makes the cadmium ion precursor solution.
Step (b): the temperature of solution is elevated to 100 ℃ logical nitrogen the time in the reaction bulb, adds 4 milliliters of aqueous solution that contain 0.41 gram sodium hydrogen selenide then, make the preceding body fluid of CdSe quantum dot.
Step (c): 20.8 gram ethyl orthosilicates are injected in the preceding body fluid of CdSe quantum dot, reacted 48 hours down, make the CdSe quantum dot of SiO 2 hybrid at 100 ℃.The CdSe quantum dot of the SiO 2 hybrid that makes issues fluorescent orange at 365 nanometer uviol lamps.
Embodiment 2:
With the cadmium acetate is the source metal of preparation quantum dot, the mercaptopropionic acid stabilizing agent, and the selenium hydrofining is the nonmetal source of preparation quantum dot, ethyl orthosilicate is a silica source, the CdSe quantum dot of preparation SiO 2 hybrid.
Step (a): in 2 liters reaction bulb, adding 0.27 gram cadmium acetate and 0.65 gram mercaptopropionic acid in 1.5 liters of deionized waters, is 10.0 with sodium hydrate regulator solution pH value, makes the cadmium ion precursor solution.
Step (b): the temperature of solution is elevated to 90 ℃ logical nitrogen the time in the reaction bulb, adds 4 milliliters of aqueous solution that contain 0.1 gram selenium hydrofining then, make the preceding body fluid of CdSe quantum dot.
Step (c): 20.8 gram ethyl orthosilicates are injected in the preceding body fluid of CdSe quantum dot, reacted 72 hours down, make the CdSe quantum dot of SiO 2 hybrid at 90 ℃.The CdSe quantum dot of the SiO 2 hybrid that makes issues red fluorescence at 365 nanometer uviol lamps.
Embodiment 3:
With the cadmium acetate is the source metal of preparation quantum dot, the TGA stabilizing agent, and sodium hydrogen selenide is the nonmetal source of preparation quantum dot, ethyl orthosilicate is a silica source, the CdSe quantum dot of preparation SiO 2 hybrid.
Step (a): in 2 liters reaction bulb, adding 4.1 gram cadmium acetates and 4.4 gram TGAs in 1.5 liters of deionized waters, is 7.5 with sodium hydrate regulator solution pH value, makes the cadmium ion precursor solution.
Step (b): the temperature of solution is elevated to 100 ℃ logical nitrogen the time in the reaction bulb, adds 4 milliliters of aqueous solution that contain 0.96 gram sodium hydrogen selenide then, make the preceding body fluid of CdSe quantum dot.
Step (c): 150 gram ethyl orthosilicates are injected in the preceding body fluid of CdSe quantum dot, reacted 24 hours down, make the CdSe quantum dot of SiO 2 hybrid at 100 ℃.The CdSe quantum dot of the SiO 2 hybrid that makes issues yellow fluorescence at 365 nanometer uviol lamps.
Embodiment 4:
With the cadmium acetate is the source metal of preparation quantum dot, the mercaptopropionic acid stabilizing agent, and sodium hydrogen selenide is the nonmetal source of preparation quantum dot, ethyl orthosilicate is a silica source, the CdSe quantum dot of preparation SiO 2 hybrid.
Step (a): in 2 liters reaction bulb, adding 1.33 gram cadmium acetates and 2.55 gram mercaptopropionic acids in 1.5 liters of deionized waters, is 9.0 with sodium hydrate regulator solution pH value, makes the cadmium ion precursor solution.
Step (b): the temperature of solution is elevated to 98 ℃ logical nitrogen the time in the reaction bulb, adds 4 milliliters of aqueous solution that contain 0.41 gram sodium hydrogen selenide then, make the preceding body fluid of CdSe quantum dot.
Step (c): 45.6 gram ethyl orthosilicates are injected in the preceding body fluid of CdSe quantum dot, reacted 0.5 hour down, make the CdSe quantum dot of SiO 2 hybrid at 98 ℃.The CdSe quantum dot of the SiO 2 hybrid that makes issues green fluorescence at 365 nanometer uviol lamps.
Embodiment 5:
With the cadmium nitrate is the source metal of preparation quantum dot, the mercaptopropionic acid stabilizing agent, and the selenium hydrofining is the nonmetal source of preparation quantum dot, ethyl orthosilicate is a silica source, the CdSe quantum dot of preparation SiO 2 hybrid.
Step (a): in 2 liters reaction bulb, adding 1.03 gram cadmium nitrates and 2.15 gram mercaptopropionic acids in 1.5 liters of deionized waters, is 9.0 with sodium hydrate regulator solution pH value, makes the cadmium ion precursor solution.
Step (b): the temperature of solution is elevated to 98 ℃ logical nitrogen the time in the reaction bulb, adds 4 milliliters of aqueous solution that contain 0.41 gram selenium hydrofining then, make the preceding body fluid of CdSe quantum dot.
Step (c): 40.2 gram ethyl orthosilicates are injected in the preceding body fluid of CdSe quantum dot, reacted 18 hours down, make the CdSe quantum dot of SiO 2 hybrid at 98 ℃.The CdSe quantum dot of the SiO 2 hybrid that makes is fluorescent orange under 365 nanometer uviol lamps.
Embodiment 6:
With the caddy is the source metal of preparation quantum dot, the mercapto glycerol stabilizing agent, and sodium hydrogen telluride is the nonmetal source of preparation quantum dot, ethyl orthosilicate is a silica source, the CdTe quantum dot of preparation SiO 2 hybrid.
Step (a): in 10 liters reaction bulb, adding 5.49 gram caddies and 11.66 gram mercapto glycerols in removing 7 liters of ionized waters, is 9.3 with potassium hydroxide regulator solution pH value, makes the cadmium ion precursor solution.
Step (b): the temperature of solution is elevated to 97 ℃ logical nitrogen the time in the reaction bulb, adds 12 milliliters of aqueous solution that contain 3.17 gram sodium hydrogen tellurides then, make the preceding body fluid of CdTe quantum dot.
Step (c): 624.7 gram ethyl orthosilicates are injected in the preceding body fluid of CdTe quantum dot, reacted 24 hours down, make the CdTe quantum dot of SiO 2 hybrid at 97 ℃.The CdTe quantum dot of the SiO 2 hybrid that makes issues yellow-green fluorescence at 365 nanometer uviol lamps.
The spectrofluorimetry of the CdTe quantum dot of the SiO 2 hybrid that embodiment 6 makes is as shown in Figure 1: emission peak is sharp-pointed and narrow, shows that the products therefrom luminescent properties is fine.
Embodiment 7:
With the caddy is the source metal of preparation quantum dot, and mercaptopropionic acid is a stabilizing agent, and sodium hydrogen telluride is the nonmetal source of preparation quantum dot, and ethyl orthosilicate is a silica source, the CdTe quantum dot of preparation SiO 2 hybrid.
Step (a): in 2 liters reaction bulb, adding 1.83 gram caddies and 4.24 gram mercaptopropionic acids in 1.3 liters of deionized waters, is 9.0 with sodium hydrate regulator solution pH value, makes the cadmium ion precursor solution.
Step (b): the temperature of solution is elevated to 98 ℃ logical nitrogen the time in the reaction bulb, adds 5 milliliters of aqueous solution that contain 1.21 gram sodium hydrogen tellurides then, make the preceding body fluid of CdTe quantum dot.
Step (c): 88.8 gram ethyl orthosilicates are injected in the preceding body fluid of CdTe quantum dot, reacted 12 hours down, make the CdTe quantum dot of SiO 2 hybrid at 98 ℃.The CdTe quantum dot of the SiO 2 hybrid that makes issues yellow fluorescence at 365 nanometer uviol lamps.
The spectrofluorimetry of the CdTe quantum dot of the SiO 2 hybrid that embodiment 7 makes is as shown in Figure 2: emission peak is sharp-pointed and narrow, shows that the products therefrom luminescent properties is fine.
The transmission electron micrograph of the CdTe quantum dot of the SiO 2 hybrid that embodiment 7 makes as shown in Figure 3, the grain diameter homogeneous, average-size is about 10 nanometers.
Embodiment 8:
Embodiment 8 just changes the caddy among the embodiment 7 into zinc chloride with embodiment 7.
Embodiment 9:
Embodiment 9 just changes the caddy among the embodiment 7 into cadmium iodide with embodiment 7, and mercaptopropionic acid changes TGA into.
Embodiment 9:
Embodiment 9 just changes the caddy among the embodiment 7 into cadmium perchlorate with embodiment 7, and sodium hydrogen telluride changes hydrogen telluride potassium into, and mercaptopropionic acid changes mercaptoethylmaine into.
Embodiment 10:
Embodiment 10 just changes the caddy among the embodiment 7 into cadmium sulfate with embodiment 7, and mercaptopropionic acid changes the sulfydryl propylamine into.
Claims (10)
1. an one kettle way prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that specifically may further comprise the steps:
Step (a): metal ion source and sulfhydryl compound are dissolved in the deionized water, the concentration of metal ion source is every liter of 0.01～300 mM, the mol ratio of sulfydryl sulfhydryl compound and metal ion source is 1～6: 1, adding hydroxide regulator solution pH value is 7～10, makes quantum dot metal ion precursor solution;
Step (b): logical nitrogen and the temperature of solution is raised to 90～100 ℃ in the quantum dot metal ion precursor solution, the nonmetallic ion source aqueous solution is injected this metal ion precursor solution, the mol ratio of nonmetallic ion source and metal ion source is 0.6～1.3: 1, makes the preceding body fluid of quantum dot;
Step (c): silica source is injected in the preceding body fluid of quantum dot, the mol ratio of silica source and metal ion source is 0.5～800: 1, reacts 0.2～108 hour down at 85～100 ℃, makes the quantum dot of SiO 2 hybrid.
2. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that the metal ion source described in the step (a) is zinc chloride, caddy, lead chloride, zinc bromide, cadmium iodide, zinc chlorate, cadmium chlorate, zinc perchlorate, cadmium perchlorate, zinc nitrate, cadmium nitrate, plumbi nitras, zinc acetate, cadmium acetate, lead acetate, zinc sulfate or cadmium sulfate.
3. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that sulfhydryl compound comprises TGA, mercaptopropionic acid, mercaptoethanol, mercaprol, mercapto glycerol, mercaptoethylmaine, sulfydryl propylamine, sulfydryl butylamine or glutathione described in the step (a).
4. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that the mol ratio of sulfydryl stabilizing agent described in the step (a) and metal ion source is 2～5: 1.
5. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that the concentration of quantum dot metal ion source in the step (a) is every liter of 0.01～200 mM.
6. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that hydroxide comprises NaOH, potassium hydroxide described in the step (a); The pH value of quantum dot metal ion prerequisite solution is 7.5～10.
7. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that the nonmetal source of the preparation quantum dot described in the step (b) comprises vulcanized sodium, potassium sulfide, sodium hydrogen telluride, hydrogen telluride potassium, sodium hydrogen selenide or selenium hydrofining.
8. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that the mol ratio of the metal ion source in middle nonmetallic ion source of step (b) and the step (a) is 0.7～1.2: 1.
9. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that used silica source comprises methyl silicate, ethyl orthosilicate, silicic acid four butyl esters or silicon tetrachloride in the step (c); The mol ratio of the metal ion source in silica source and the step (a) is 1～600: 1.
10. a kind of one kettle way according to claim 1 prepares the method for the quantum dot of SiO 2 hybrid, it is characterized in that the reaction time is 0.5～72 hour in the step (c).
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