CN102268262B - Method for synthesizing Pt: ZnSe(S) alloy nano crystal by aqueous phase process - Google Patents
Method for synthesizing Pt: ZnSe(S) alloy nano crystal by aqueous phase process Download PDFInfo
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000956 alloy Substances 0.000 title claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000008346 aqueous phase Substances 0.000 title abstract description 5
- 239000002159 nanocrystal Substances 0.000 title abstract description 5
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 30
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003637 basic solution Substances 0.000 claims description 7
- 230000005587 bubbling Effects 0.000 claims description 7
- 238000006392 deoxygenation reaction Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000011835 investigation Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- -1 sulfhydryl compound Chemical class 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract 2
- 239000012445 acidic reagent Substances 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 150000003057 platinum Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000006862 quantum yield reaction Methods 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
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- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 231100000053 low toxicity Toxicity 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
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- 229910004613 CdTe Inorganic materials 0.000 description 1
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- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000005859 cell recognition Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- ZHNFLHYOFXQIOW-LPYZJUEESA-N quinine sulfate dihydrate Chemical compound [H+].[H+].O.O.[O-]S([O-])(=O)=O.C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21.C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 ZHNFLHYOFXQIOW-LPYZJUEESA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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Abstract
The invention belongs to the technical field of preparation methods of nano luminescent materials, and in particular relates to a method for synthesizing a Pt: ZnSe(S) alloy nano crystal by an aqueous phase process. The method comprises the step of preparing a water-soluble Pt: ZnSe(S) alloy nano crystal by using ultrapure water as a solvent, as well as inorganic metal water-soluble compounds such as zinc salt, platinum salt and the like, a selenium powder and a carboxylic acid reagent containing a sulfydryl group as raw materials. According to the invention, cheap raw materials are used instead of an expensive and dangerous organic metal precursor, thus the method is environmentally-friendly, and the preparation cost is reduced; the operation is simple, safe and good in repeatability; and the synthesized nano crystal has a good crystal form and uniform size.
Description
Technical field
The present invention relates to a kind of nano luminescent material preparation method, adopt the water method to synthesize water-soluble Pt:ZnSe (S) alloy nanometer crystals.
Background technology
Semiconductor nano, have that quantum yield is high, the exciting light spectrum width and continuously, emmission spectrum is symmetrical and narrow, radiative color with characteristics such as change of size, photochemical stability are good, compare with traditional fluorescence dye and have incomparable superiority.If can solve the problems such as its biology mixes, bio-toxicity, quantum dot will be in the huge effect of the aspects such as migration of cell recognition, cell dyeing, medical diagnosis on disease, Real Time Monitoring biological components performance.Along with progressively going deep into of research, semiconductor nano becomes emerging, the forward position, the most active research field in analysis science as biomarker.
Semiconductor nano (CdSe, CdS, CdTe) take the Cd compounds as representative has carried out a large amount of research as fluorescent marker in the application of biological field at present, make in the application such as its biology in future, medical science, pharmacy and exist hidden danger but this class contains toxicity that the quantum dot of cadmium has, therefore, the new low toxicity quantum dot of exploitation is used for biomarker becomes the interested problem of people.And the nanocrystalline good luminescent properties that may overcome the problem of bio-toxicity and can keep semiconductor nano material of the ZnSe of containing transition metal ion.Adopted around the nanocrystalline preparation of doping type ZnSe at present is the organic synthesis method more, although the Doped nanocrystal of preparation has the advantages such as fluorescence quantum yield is high, monodispersity is good, but this semiconductor nano is oil-soluble, and most of biomolecules are water miscible, and this has just limited its application at biomedical aspect to a great extent.Compare water phase synthesis method good reproducibility, cheapness, low toxicity, and synthetic nanocrystalline have good stability and biocompatibility with the organic synthesis route.
At present, nanocrystalline at the transient metal doped ZnSe of synthesizing water-solubility and be applied to be in the world initial period aspect the research of biomarker.2009, the method that the people such as the Su Xingguang of Jilin University adulterate by nucleation successfully synthesized water miscible Mn:ZnSe nanocrystalline (Chinese patent: application number is 200910066651.X) at aqueous phase.Their method is, at first generates the MnSe nucleus that has stablizer to coat, then carries out the growth of ZnSe shell around the MnSe nucleus, and molten interface is very thin mutually to cause the Mn/Zn ion, quantum yield very low (only having 2.4%).2011, the Su Xingguang seminar of Jilin University by the mode of grow doping synthesized water miscible Cu:ZnSe nanocrystalline (G Xue, W Chao, N Lu, SX Guang.J.Lumin., 2011,131,1300-1304.).The emmission spectrum of Cu:ZnSe quantum dot changes between 465nm～495nm along with red shift has occured in the prolongation of return time, and fluorescence quantum yield has reached 2.6%.2011, the people such as the Wang Hongzhi of Donghua University utilized the approach of nucleation doping to synthesize Mn:ZnSe nanocrystalline (Chinese patent: application number is 201010287997.5) at aqueous phase.They are by extending the ZnSe epitaxially grown time of shell, have obtained the nanocrystalline of the adjustable stabilized illumination of color, and its emmission spectrum changes between 572～602nm, and fluorescence quantum yield has reached 4.8%.According to literature survey, the transient metal doped ZnSe of synthesizing water-solubility is nanocrystalline, and its fluorescence quantum yield is generally lower.Therefore, exploring a kind of synthetic method tool that improves the nanocrystalline fluorescence efficiency of water soluble ZnSe and photochemical stability is of great significance.
In addition, Pang Daiwen seminar synthesized the CdSe of doping Pt nanocrystalline (Z Q Tian, Z L Zhang, D W Pang, et al.Chem.Commun., 2009,4025-4027.), have the advantages such as size is little, structure homogeneous, good stability.And with Pt mix ZnSe nanocrystalline in from having no the bibliographical information mistake.For this reason, we with transition metal Pt mix ZnSe nanocrystalline in, utilize the water method synthetic, expectation improves nanocrystalline luminous efficiency and the photochemical stability of water soluble ZnSe.
Summary of the invention
Purpose of the present invention is exactly for the general lower problem of the nanocrystalline fluorescence quantum yield of water-soluble transition metal doped ZnS e, proposes a kind of water method and synthesizes the nanocrystalline method of transition metal Pt doped ZnS e.Water-soluble Pt:ZnSe (S) the alloy nanometer crystals good crystalline, the size homogeneous that synthesize.The method has the advantages such as reaction system is simple, raw material is easy to get, environmental pollution is little.
For achieving the above object, the present invention is at synthetic Pt:ZnSe (S) alloy nanometer crystals of aqueous phase, with water-soluble sulfhydryl compound as tensio-active agent, by extending the reaction times, the nanocrystalline degree of crystallinity of gained is better, the size homogeneous, fluorescence quantum yield (take Quinine Sulphate Di HC as reference) is in 4.7% left and right.
The method of synthetic Pt:ZnSe (S) alloy nanometer crystals of water method of the present invention specifically comprises the steps:
1, at first zinc salt and water-soluble sulfhydryl compound are mixed thin up to 50 in the there-necked flask of 250ml～100ml, mix and blend 5～20 minutes;
Zinc salt is Zn (NO
3)
2, Zn (Ac)
2Or ZnCl
2, water-soluble sulfhydryl compound is Thiovanic acid, 3-thiohydracrylic acid, sulfydryl butyric acid or halfcystine, the ratio of zinc salt and water-soluble sulfhydryl compound is 1: 1～1: 5.
2, add 10ml Tetrachloroplatinum solution in the solution of step 1, continue to stir 5 minutes;
The concentration of Tetrachloroplatinum solution is 0.001M～0.01M.
3, with sodium hydroxide solution, the pH value of solution of step 2 is transferred to 8～11, pass into rare gas element this moment in this basic solution, and bubbling deoxygenation 10～30 minutes obtains oxygen-free water solution;
Rare gas element can be argon gas or nitrogen.
4, under protection of inert gas, selenium powder and sodium borohydride are dissolved in 1～20ml ultrapure water, be heated to 40～80 ℃, reacted 1～30 minute, make the NaHSe storing solution;
The mol ratio of selenium powder and sodium borohydride is 1: 2～1: 10, and the mol ratio of selenium powder and zinc salt is 1: 2～1: 15.
5, the NaHSe storing solution that step 4 is made is injected in the alkaline oxygen-free water solution that step 3 makes fast;
6, the solution that makes of step 5 begins to heat up under protection of inert gas, begins timing when temperature rises to 96 ℃.At set intervals, take out certain solution with glass syringe, be used for ultraviolet and fluorometric investigation.Reaction finishes to treat that it naturally cools to room temperature, can obtain ZnSe (S) the alloy nanometer crystals aqueous solution of faint yellow transparent doping Pt.
7, add Virahol in the solution that makes to step 6, centrifugal purification then, vacuum-drying obtains Pt:ZnSe (S) alloy nanometer crystals powder.
The method of synthetic Pt:ZnSe (S) alloy nanometer crystals of water method of the present invention has following characteristics:
1, transition metal Pt is doped in ZnSe (S) alloy nanometer crystals first.
2, adopt synthesizing nanocrystalline in the aqueous solution, compare the synthetic method of organic phase, toxicity and cost all reduce greatly, and the single sintering amount is large, are fit to large-scale preparation.In addition, synthetic nanocrystalline good water solubility and stable does not need aftertreatment can be directly used in biomarker.
3, in the X-ray diffraction spectrogram, with discovery after the standard card contrast, the peak position of the nanocrystalline diffraction peak of gained is between the peak position of the nanocrystalline and diffraction peak that Cubic ZnS is nanocrystalline of the Cubic ZnSe of standard, show gained nanocrystalline be not simple Pt:ZnSe, but Pt:ZnSe (S) alloy nanometer crystals.
4, in fluorescence spectrum, the position of emission peak appears at the 470nm left and right.
Water-soluble doping type low toxicity Pt:ZnSe (S) alloy nanometer crystals that the present invention synthesizes can be used as the fluorescent mark material, is widely used in biological detection, in cell, tissue or even living imaging research.
Below in conjunction with drawings and Examples, technical scheme of the present invention is further described.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of Pt:ZnSe (S) alloy nanometer crystals that synthesizes when the reaction times is 11h of the present invention.
Fig. 2 is the TEM figure of Pt:ZnSe (S) alloy nanometer crystals that synthesizes when the reaction times is 11h of the present invention.
Fig. 3 is that the excitation wavelength of Pt:ZnSe (S) alloy nanometer crystals that synthesizes in the differential responses time of the present invention is the fluorescence spectrum figure of 350nm.
Embodiment
Embodiment 1
1, at first 0.439g zinc acetate and 1.0614g 3-thiohydracrylic acid are mixed, in the there-necked flask of 250ml thin up to 50ml, mix and blend 5 minutes.
2, the Tetrachloroplatinum solution that adds 10ml0.001M in the solution of step 1 continues to stir 5 minutes.
3, with sodium hydroxide solution, the pH value of solution of step 2 is transferred to 8, pass into argon gas this moment in this basic solution, and bubbling deoxygenation 10 minutes obtains oxygen-free water solution.
4, under argon shield, 0.079g selenium powder and 0.0757g sodium borohydride are dissolved in the 5ml ultrapure water, be heated to 40 ℃, reacted 30 minutes, make the NaHSe storing solution.
5, the NaHSe storing solution that step 4 is made is injected in the alkaline oxygen-free water solution that step 3 makes fast.
6, the solution that makes of step 5 begins to heat up under protection of inert gas, begins timing when temperature rises to 96 ℃.At set intervals, take out certain solution with glass syringe, be used for ultraviolet and fluorometric investigation.Reaction finishes to treat that it naturally cools to room temperature, can obtain ZnSe (S) the alloy nanometer crystals aqueous solution of faint yellow transparent doping Pt.
7, add Virahol in the solution that makes to step 6, centrifugal purification then, vacuum-drying obtains Pt:ZnSe (S) alloy nanometer crystals powder.
1, at first 0.6585g zinc acetate and 0.9553g 3-thiohydracrylic acid are mixed, in the there-necked flask of 250ml thin up to 60ml, mix and blend 10 minutes.
2, the Tetrachloroplatinum solution that adds 10ml0.002M in the solution of step 1 continues to stir 5 minutes.
3, with sodium hydroxide solution, the pH value of solution of step 2 is transferred to 9, pass into argon gas this moment in this basic solution, and bubbling deoxygenation 20 minutes obtains oxygen-free water solution.
4, under argon shield, 0.079g selenium powder and 0.1136g sodium borohydride are dissolved in the 1ml ultrapure water, be heated to 50 ℃, reacted 1 minute, make the NaHSe storing solution.
5, the NaHSe storing solution that step 4 is made is injected in the alkaline oxygen-free water solution that step 3 makes fast.
6, the solution that makes of step 5 begins to heat up under protection of inert gas, begins timing when temperature rises to 96 ℃.At set intervals, take out certain solution with glass syringe, be used for ultraviolet and fluorometric investigation.Reaction finishes to treat that it naturally cools to room temperature, can obtain ZnSe (S) the alloy nanometer crystals aqueous solution of faint yellow transparent doping Pt.
7, add Virahol in the solution that makes to step 6, centrifugal purification then, vacuum-drying obtains Pt:ZnSe (S) manocrystalline powders.
Embodiment 3
1, at first 1.0975g zinc acetate and 1.0614g 3-thiohydracrylic acid are mixed, in the there-necked flask of 250ml thin up to 70ml, mix and blend 15 minutes.
2, the Tetrachloroplatinum solution that adds 10ml0.004M in the solution of step 1 continues to stir 5 minutes.
3, with sodium hydroxide solution, the pH value of solution of step 2 is transferred to 9.5, pass into nitrogen this moment in this basic solution, and bubbling deoxygenation 15 minutes obtains oxygen-free water solution.
4, under nitrogen protection, 0.079g selenium powder and 0.1514g sodium borohydride are dissolved in the 20ml ultrapure water, be heated to 80 ℃, reacted 5 minutes, make the NaHSe storing solution.
5, the NaHSe storing solution that step 4 is made is injected in the alkaline oxygen-free water solution that step 3 makes fast.
6, the solution that makes of step 5 begins to heat up under protection of inert gas, begins timing when temperature rises to 96 ℃.At set intervals, take out certain solution with glass syringe, be used for ultraviolet and fluorometric investigation.Reaction finishes to treat that it naturally cools to room temperature, can obtain ZnSe (S) the alloy nanometer crystals aqueous solution of faint yellow transparent doping Pt.
7, add Virahol in the solution that makes to step 6, centrifugal purification then, vacuum-drying obtains Pt:ZnSe (S) alloy nanometer crystals powder.
Embodiment 4
1, at first 2.195g zinc acetate and 4.2456g 3-thiohydracrylic acid are mixed, in the there-necked flask of 250ml thin up to 80ml, mix and blend 15 minutes.
2, the Tetrachloroplatinum solution that adds 10ml0.006M in the solution of step 1 continues to stir 5 minutes.
3, with sodium hydroxide solution, the pH value of solution of step 2 is transferred to 10, pass into nitrogen this moment in this basic solution, and bubbling deoxygenation 20 minutes obtains oxygen-free water solution.
4, under nitrogen protection, 0.079g selenium powder and 0.1893g sodium borohydride are dissolved in the 20ml ultrapure water, be heated to 50 ℃, reacted 25 minutes, make the NaHSe storing solution.
5, the NaHSe storing solution that step 4 is made is injected in the alkaline oxygen-free water solution that step 3 makes fast;
6, the solution that makes of step 5 begins to heat up under protection of inert gas, begins timing when temperature rises to 96 ℃.At set intervals, take out certain solution with glass syringe, be used for ultraviolet and fluorometric investigation.Reaction finishes to treat that it naturally cools to room temperature, can obtain ZnSe (S) the alloy nanometer crystals aqueous solution of faint yellow transparent doping Pt.
7, add Virahol in the solution that makes to step 6, centrifugal purification then, vacuum-drying obtains Pt:ZnSe (S) alloy nanometer crystals powder.
Embodiment 5
1, at first 3.2925g zinc acetate and 1.5921g 3-thiohydracrylic acid are mixed, in the there-necked flask of 250ml thin up to 100ml, mix and blend 20 minutes.
2, the Tetrachloroplatinum solution that adds 10ml0.01M in the solution of step 1 continues to stir 5 minutes.
3, with sodium hydroxide solution, the pH value of solution of step 2 is transferred to 11, pass into rare gas element this moment in this basic solution, and bubbling deoxygenation 30 minutes obtains oxygen-free water solution.
4, under argon shield, 0.079g selenium powder and 0.3785g sodium borohydride are dissolved in the 10ml ultrapure water, be heated to 60 ℃, reacted 20 minutes, make the NaHSe storing solution.
5, the NaHSe storing solution that step 4 is made is injected in the alkaline oxygen-free water solution that step 3 makes fast.
6, the solution that makes of step 5 begins to heat up under protection of inert gas, begins timing when temperature rises to 96 ℃.At set intervals, take out certain solution with glass syringe, be used for ultraviolet and fluorometric investigation.Reaction finishes to treat that it naturally cools to room temperature, can obtain ZnSe (S) the alloy nanometer crystals aqueous solution of faint yellow transparent doping Pt.
7, add Virahol in the solution that makes to step 6, centrifugal purification then, vacuum-drying obtains Pt:ZnSe (S) alloy nanometer crystals powder.
Claims (4)
1. the method for synthetic Pt:ZnSe (S) alloy nanometer crystals of water method, specifically comprise the steps:
(1) at first zinc salt and water-soluble sulfhydryl compound are mixed, thin up to 50 in the there-necked flask of 250ml～100ml, mix and blend 5～20 minutes, the mol ratio of zinc salt and water-soluble sulfhydryl compound is 1: 1～1: 5;
(2) adding 10ml concentration in the solution of step (1) is the Tetrachloroplatinum solution of 0.001mol/L～0.01mol/L, continues to stir 5 minutes;
(3) with sodium hydroxide solution, the pH value of solution of step (2) is transferred to 8～11, pass into argon gas or nitrogen this moment in this basic solution, and bubbling deoxygenation 10～30 minutes obtains oxygen-free water solution;
(4) under argon gas or nitrogen protection, selenium powder and sodium borohydride are dissolved in 1～20ml ultrapure water, be heated to 40～80 ℃, reacted 1～30 minute, make the NaHSe storing solution, the mol ratio of selenium powder and sodium borohydride is 1: 2～1: 10;
(5) the NaHSe storing solution that step (4) is made is injected in the alkaline oxygen-free water solution that step (3) makes fast;
(6) solution that makes of step (5) begins to heat up under argon gas or nitrogen protection, when rising to 96 ℃, temperature begins timing, at set intervals, take out certain solution with glass syringe, be used for ultraviolet and fluorometric investigation, reaction finishes to treat that it naturally cools to room temperature, can obtain ZnSe (S) the alloy nanometer crystals aqueous solution of faint yellow transparent doping Pt;
(7) add Virahol in the solution that makes to step (6), centrifugal purification then, vacuum-drying obtains Pt:ZnSe (S) alloy nanometer crystals powder.
2. a kind of water method as claimed in claim 1 is synthesized the method for Pt:ZnSe (S) alloy nanometer crystals, it is characterized in that: in described step (1), zinc salt is Zn (NO
3)
2, Zn (Ac)
2Or ZnCl
2
3. a kind of water method as claimed in claim 1 is synthesized the method for Pt:ZnSe (S) alloy nanometer crystals, and it is characterized in that: in described step (1), water-soluble sulfhydryl compound is Thiovanic acid, 3-thiohydracrylic acid, sulfydryl butyric acid or halfcystine.
4. a kind of water method as claimed in claim 1 is synthesized the method for Pt:ZnSe (S) alloy nanometer crystals, it is characterized in that: in described step (1) and step (4), the mol ratio of selenium powder and zinc salt is 1: 2～1: 15.
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