CN100497163C - Compound alkali metal hydrate dissolvent synthesis method for metallic sulfide nano crystal material - Google Patents
Compound alkali metal hydrate dissolvent synthesis method for metallic sulfide nano crystal material Download PDFInfo
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- CN100497163C CN100497163C CNB2007100786419A CN200710078641A CN100497163C CN 100497163 C CN100497163 C CN 100497163C CN B2007100786419 A CNB2007100786419 A CN B2007100786419A CN 200710078641 A CN200710078641 A CN 200710078641A CN 100497163 C CN100497163 C CN 100497163C
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Abstract
The invention discloses a preparation method for a metal sulfide and a composite metal sulfide nano crystal material, which is suitable for the preparation of the nano crystal materials of cadmium sulfide, cuprous sulfide, zinc sulfide, lead sulfide, bismuth sulfide, and zinc-cadmium sulfide. The method is characterized in that water or organic solvent used in the existing hydrothermal or solvent thermal synthetic methods is replaced with melt composite alkali metal hydroxide which is synthesized through a chemical reaction under the normal atmosphere and a temperature between 100 and 300 DEG C. The raw materials used are soluble inorganic metal salts and sulfide or sulfide compounds, thereby having less controllable parameters and simple art, and being able to amplify manufacturing during the process of synthesis. Metal sulfide crystal produced has the advantages of good crystal, clean surface and even size, and is suitable for the research on the intrinsic properties and the maximum play of the functions of the nano crystal materials. The metal sulfide and the composite metal nano crystal materials have properties of a semiconductor, LED and optoelectronic, thereby being suitable for biomarker and preparation of a nano electronic apparatus, an LED apparatus and an optoelectronic apparatus.
Description
Technical field
The invention belongs to the preparation field of metal sulfide nanocrystal material, specifically, relating to a kind of is the metallic oxide nanocrystal body preparation methods of solvent with the composite alkali metal oxide compound.
Background technology
The metal sulfide nanocrystal material has semi-conductor, luminous and photoelectric property, can be used for biomarker, preparation nano electron device, luminescent device and photoelectric device.In the method for existing synthesizing sulfide, the method of double solvents thermal synthesis, for example the Chinese patent publication number is that 200510103028.9 methods that prepare the sulfide nanoparticle adopt oxyhydroxide, lipid acid and multiple organic polar solvent mix as synthetic, with metal-salt and sodium sulphite is synthesis material, preparation feedback forerunner at first, mix with a small amount of oleic acid as certain sodium hydroxide, add behind the ethanolic soln mixing 30min stand-by again, certain soluble metal salt is dissolved in an amount of aqueous solution, certain sodium sulphite is dissolved in an amount of aqueous solution, then these solvents are added successively to insert behind the reactor and carry out reacting by heating in the autoclave, synthesize multiple sulfide nano crystal material.The relating to high pressure and use autoclave vessel in building-up process of this method,, the building-up process controllable parameter is more, causes the synthetic cost higher.Adopt lipid acid to cause nano-material surface unclean in addition, be difficult to realize research and further finishing the nano crystal material intrinsic properties.Liu Hong, Hu Chenguo and Wang Zhonglin had reported in 2006 once that composite alkali metal oxyhydroxide mediator method synthesized complex oxide (Nano Letters, 6,1535) method, it is reaction solvent that this method adopts fused composite alkali metal oxyhydroxide, and metal inorganic salt and oxide compound are reaction raw materials synthetic complex oxide and other oxygenatedchemicalss under low-temperature atmosphere-pressure.Yet there are no report for preparing sulfide nano crystal with composite alkali metal oxyhydroxide mediator method.
Summary of the invention
The present invention is directed to the deficiency in the existing double solvents thermal synthesis sulfide nano crystal material technology, and provide a kind of reactant at low temperature, reaction process is under the normal pressure, is the metallic oxide nanocrystal body preparation methods of solvent with the composite alkali metal oxide compound.
The composite alkali metal hydrate dissolvent synthesis method reaction of metal sulfide nanocrystal material of the present invention is synthetic as follows successively:
Step 2 preparation reaction raw materials: choose any one kind of them or metal soluble salt that two kinds contain zinc or cadmium or bismuth or lead or copper, join and be taken as 10～90% of reaction raw materials weight percent,, join and be taken as 10～90% of reaction raw materials weight percent as the reaction raw materials that sulfonium ion is provided with sulphur powder or sulfide;
Step 3 reacting by heating: with reaction solvent and reaction raw materials insert in the reaction vessel, reaction solvent and reaction raw materials respectively account for whole 50%～99.5% and 0.5%～50% of the reactive material total weight percent of inserting, add a cover sealing, then reaction vessel is put into the heating installation that is heated to 100～300 ℃, pre-hot melt 20～60 minutes, after the interior solid complex hydroxide of reactor is melted fully, reaction vessel is opened, stir with agitator, make reactant uniform distribution in the reaction solvent of molten state, closed container once more, and under the state of 100～300 ℃ of constant temperature, continue heating 1～100 hour;
Step 4 cooling: the reaction vessel after the isothermal reaction is cooled to room temperature;
Step 5 washing: earlier reaction product is dissolved earlier with cold/hot deionized water, be 1000～20000 rev/mins whizzer with rotating speed again or filter with pumping and filtering device, then centrifugal or filtering product is disperseed in cold or hot deionized water again, repeating then to dewater and clean 3～5 times, is neutral until the pH of reaction product value.
Described reaction vessel and agitator are for to have the inert material preparation to alkali metal hydroxide.Heating installation be one of retort furnace, resistance furnace, baking oven can controlled temperature heating installation.The present invention's synthetic being more prone to more convenient to operate realized.Reaction product is identified crystalline phase with X-ray diffraction (XRD), characterize its pattern and size with scanning electron microscope or transmission electron microscope.
Adopt the synthetic metal sulfide nanocrystal material of complex hydroxide solvent method of the present invention only to need to carry out chemosynthesis under normal pressure, synthesis temperature is at 100-300 ℃.The raw material that is adopted is cheap inorganic metal salt and sulphur powder or sulfocompound, because be one-step synthesis, promptly raw material and reaction solvent are inserted the reaction of heating in the constant temperature oven after once adding reactor, and controllable parameter is less in the building-up process, and synthetic cost is low.Crystal freely disperses development growth in liquation, resulting metallic sulfide crystalline material generally has the profile of rule, and advantages of good crystallization.Because do not introduce tensio-active agent or template, the surface cleaning of nano crystal material is fit to its function of carrying out the research of intrinsic performance and bringing into play nano crystal material is to greatest extent also carried out simultaneously surface modification easily in building-up process.The present invention can also be by changing batching, synthetic complex sulfide nano crystal material.
Advantage: the synthetic metal sulfide nanocrystal material of complex hydroxide solvent method of the present invention only needs to carry out chemosynthesis under normal pressure, and synthesis temperature is at 100-300 ℃.The raw material that is adopted is cheap inorganic metal salt and sulphur powder or sulfocompound, because be one-step synthesis, promptly raw material and reaction solvent are inserted the reaction of heating in the constant temperature oven after once adding reactor, and controllable parameter is less in the building-up process, and synthetic cost is low.Crystal freely disperses development growth in liquation, resulting metallic sulfide crystalline material generally has the profile of rule, and advantages of good crystallization.Because do not introduce tensio-active agent or template, the surface cleaning of nano crystal material is fit to its function of carrying out the research of intrinsic performance and bringing into play nano crystal material is to greatest extent also carried out simultaneously surface modification easily in building-up process.The present invention can also be by changing batching, synthetic complex sulfide nano crystal material.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the inventive method synthetic cadmium sulfide nanostructure;
Fig. 2 is the inventive method synthetic cadmium sulfide nanostructure scanning electron microscope diagram;
Fig. 3 is the x-ray diffraction pattern of the inventive method synthetic zinc sulfide nano structure;
Fig. 4 is the inventive method synthetic zinc sulfide nano structure scanning electron microscope diagram;
Fig. 5 is the x-ray diffraction pattern of the inventive method synthetic lead sulfide nanostructure;
Fig. 6 is the scanning electron microscope diagram of the inventive method synthetic lead sulfide nanostructure;
Fig. 7 is the x-ray diffraction pattern of the inventive method synthetic cuprous sulfide nanostructure;
Fig. 8 is the scanning electron microscope diagram of the inventive method synthetic cuprous sulfide nanostructure;
Fig. 9 is the x-ray diffraction pattern of the inventive method synthetic bismuth sulfide nano structure;
Figure 10 is the scanning electron microscope diagram of the inventive method synthetic bismuth sulfide nano structure;
Figure 11 is the x-ray diffraction pattern of the inventive method synthetic zinc-cadmium sulfide nanostructure;
The scanning electron microscope diagram of Figure 12 the inventive method synthetic zinc-cadmium sulfide nanostructure.
Embodiment
The concrete synthetic method of Cadmium Sulfide (CdS) nano crystal material
1, KOH=57% and NaOH=43% weighing by weight percentage mixes as reaction solvent.
2, press Cadmium chloride fine powder (CdCl
2) be respectively 23% and 77% weighing as reactant with the weight percent of sulphur powder.The weight of reactant and the weight percent of reactant+reaction solvent are 2.2%.
3, the reaction raw materials and the reaction solvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the tetrafluoroethylene reaction vessel, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature retort furnace.After making reaction vessel in stove, be incubated 40 minutes, open reaction vessel and stir reaction solvent and the reactant uniform mixing that makes molten state.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 24 hours.
4, reaction vessel is taken out from retort furnace, be chilled to room temperature naturally.
5, reaction product is dissolved with deionized water, aaerosol solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeating above-mentioned steps 5 times, is neutral until reaction product pH value.
Synthetic product is the Cadmium Sulfide of single-phase hexagonal crystallographic texture as shown in Figure 1.The Cadmium Sulfide crystal is wide as shown in Figure 2 is that 200 nanometers～10 micron, length are several 10 to 100 microns linear structures.
Embodiment 2:
Synthesizing of zinc sulphide (ZnS) nanocrystalline structure
1. KOH=57% and NaOH=43% weighing by weight percentage mixes as reaction solvent.
2. press zinc acetate (Zn (CH
3COO)
22H
2O) with sodium sulphite (Na
2S.9H
2O) weight percent is respectively 16% and 84% weighing as reactant.The weight of reactant and the weight percent of reactant+reaction solvent are 10%.
3. the reaction raw materials and the reaction solvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the tetrafluoroethylene reaction vessel, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature retort furnace.After making reaction vessel in stove, be incubated 40 minutes, open reaction vessel and stir reaction solvent and the reactant uniform mixing that makes molten state.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 41 hours.
4. reaction vessel is taken out from retort furnace, be chilled to room temperature naturally.
5. reaction product is dissolved with deionized water, aaerosol solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeating above-mentioned steps 5 times, is neutral until reaction product pH value.
Synthetic product is the zinc sulphide of single-phase hexagonal crystallographic texture as shown in Figure 3.Be illustrated in figure 4 as transmission electron microscope figure observation and show that zinc sulfide crystal is for being of a size of 300～500 nano flower-like structures.
Embodiment 3:
The synthetic method of lead sulfide (PbS) nano crystal material
1. KOH=57% and NaOH=43% weighing by weight percentage mixes as reaction solvent.
2. press lead nitrate (Pb (NO
3)
2) and sodium sulphite (Na
2S.9H
2O) weight percent is respectively 42% and 58% weighing as reactant.The weight of reactant and the weight percent of reactant+reaction solvent are 1.3%.
3. the reaction raw materials and the reaction solvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the tetrafluoroethylene reaction vessel, will gather then four not the ethene container add a cover sealing to insert temperature be in 165 ℃ the constant temperature retort furnace.After making reaction vessel in stove, be incubated 40 minutes, open reaction vessel and stir reaction solvent and the reactant uniform mixing that makes molten state.Add a cover closed reaction vessel once more, and under the state of 165 ℃ of constant temperature, continue insulation 12 hours.
4. reaction vessel is taken out from retort furnace, be chilled to room temperature naturally.
5. reaction product is dissolved with deionized water, aaerosol solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeating above-mentioned steps 5 times, is neutral until reaction product pH value.
Synthetics is the lead sulfide of single-phase cubic crystal structure as shown in Figure 5.The lead sulfide crystalline size is 100～120 nanoparticle structure as shown in Figure 6.
Embodiment 4:
Cuprous sulfide (Cu
2S) synthetic method of nano crystal material
1. KOH=57% and NaOH=43% weighing by weight percentage mixes as reaction solvent.
2. press lead nitrate (Pb (NO
3)
2) and sodium sulphite (Na
2S.9H
2O) weight percent is respectively 22% and 88% weighing as reactant.The weight of reactant and the weight percent of reactant+reaction solvent are 1.3%.
3. the reaction raw materials and the reaction solvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the tetrafluoroethylene reaction vessel, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature retort furnace.After making reaction vessel in stove, be incubated 40 minutes, open reaction vessel and stir reaction solvent and the reactant uniform mixing that makes molten state.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 24 hours.
4. reaction vessel is taken out from retort furnace, be chilled to room temperature naturally.
5. reaction product is dissolved with deionized water, aaerosol solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeating above-mentioned steps 5 times, is neutral until reaction product pH value.
Synthetics is the cuprous sulfide of single-phase cubic crystal structure as shown in Figure 7.The cuprous sulfide crystal diameter is that 50～300 nanometers, length are the club shaped structure of 3-6 micron as shown in Figure 8.
Embodiment 5:
Bismuth sulfide (Bi
2S
3) synthetic method of nanocrystalline structure
1. KOH=57% and NaOH=43% weighing by weight percentage mixes as reaction solvent.
2. press Bismuth trinitrate (Bi (NO)
3.5H
2O) with sodium sulphite (Na
2S.9H
2O) weight percent is respectively 57% and 43% weighing as reactant.The weight of reactant and the weight percent of reactant+reaction solvent are 1.8%.
3. the reaction raw materials and the reaction solvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the tetrafluoroethylene reaction vessel, will gather then four not the ethene container add a cover sealing to insert temperature be in 165 ℃ the constant temperature retort furnace.After making reaction vessel in stove, be incubated 40 minutes, open reaction vessel and stir reaction solvent and the reactant uniform mixing that makes molten state.Add a cover closed reaction vessel once more, and under the state of 165 ℃ of constant temperature, continue insulation 6 hours.
4. reaction vessel is taken out from retort furnace, be chilled to room temperature naturally.
5. reaction product is dissolved with deionized water, aaerosol solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeating above-mentioned steps 5 times, is neutral until reaction product pH value.
Synthetics is the bismuth sulfide of single-phase rhombic system as shown in Figure 9.The bismuth sulfide crystal diameter is that 50～300 nanometers, length are 3～6 microns club shaped structure as shown in figure 10.
Embodiment 6:
Zinc-cadmium sulfide (Zn
0.2Cd
0.8S) nanocrystalline structure is synthetic
1. KOH=57% and NaOH=43% weighing by weight percentage mixes as reaction solvent.
2. press zinc acetate (Zn (CH
3COO)
22H
2O) weight percent=29%, Cadmium Sulfide (CdCl
22.5H
2O) weight percent=22%, sodium sulphite (Na
2S.9H
2O) weight percent=49% weighing is as reactant.The weight of reactant and the weight percent of reactant+reaction solvent are 2.3%.
3. the reaction raw materials and the reaction solvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the tetrafluoroethylene reaction vessel, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature retort furnace.After making reaction vessel in stove, be incubated 40 minutes, open reaction vessel and stir reaction solvent and the reactant uniform mixing that makes molten state.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 30 hours.
4. reaction vessel is taken out from retort furnace, be chilled to room temperature naturally.
5, reaction product is dissolved with deionized water, aaerosol solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeating above-mentioned steps 5 times, is neutral until reaction product pH value.
Synthetics is the zinc-cadmium sulfide of single-phase hexagonal structure as shown in figure 11.The zinc-cadmium sulfide diameter is that 100～120 nanometers, length are 10～100 microns linear structure as shown in figure 12.
Claims (3)
1, a kind of composite alkali metal hydrate dissolvent synthesis method of metal sulfide nanocrystal material is characterized in that: synthetic according to the following steps successively:
Step 1 preparation reaction solvent: 2 kinds of alkali metal hydroxides in optional solid-state lithium hydroxide, sodium hydroxide, the potassium hydroxide, uniform mixing under the situation of not adding any aqueous solution, it all is respectively 10～90% of reaction solvent weight percent;
Step 2 preparation reaction raw materials: choose any one kind of them or metal soluble salt that two kinds contain zinc or cadmium or bismuth or lead or copper, join and be taken as 10～90% of reaction raw materials weight percent,, join and be taken as 10～90% of reaction raw materials weight percent as the reaction raw materials that sulfonium ion is provided with sulphur powder or sulfide;
Step 3 reacting by heating: reaction solvent and reaction raw materials are inserted in the reaction vessel, reaction solvent and reaction raw materials respectively account for whole 50%～99.5% and 0.5%～50% of the reactive material total weight percent of inserting, add a cover sealing, then reaction vessel is put into the heating installation that is heated to 100～300 ℃, pre-hot melt 20～60 minutes, after the interior solid complex hydroxide of reactor is melted fully, reaction vessel is opened, stir with agitator, make reactant uniform distribution in the reaction solvent of molten state, closed container once more, and under the state of 100～300 ℃ of constant temperature, continue heating 1～100 hour;
Step 4 cooling: the reaction vessel after the isothermal reaction is cooled to room temperature;
Step 5 washing: earlier reaction product is dissolved earlier with cold/hot deionized water, be 1000～20000 rev/mins whizzer with rotating speed again or filter with pumping and filtering device, then centrifugal or filtering product is disperseed in cold or hot deionized water again, repeating then to dewater and clean 3～5 times, is neutral until the pH of reaction product value.
2, the composite alkali metal hydrate dissolvent synthesis method of metal sulfide nanocrystal material according to claim 1, it is characterized in that: described reaction vessel and agitator are for to have the inert material preparation to alkali metal hydroxide.
3, the composite alkali metal hydrate dissolvent synthesis method of metal sulfide nanocrystal material according to claim 1 is characterized in that: described heating installation be one of retort furnace, resistance furnace, baking oven can controlled temperature heating installation.
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| CN101866960B (en) * | 2010-02-10 | 2011-12-14 | 中国科学院上海硅酸盐研究所 | Method for preparing CdS-Bi2S3 composite nanocrystalline by utilizing partial cation exchange reaction |
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| CN103243390B (en) * | 2013-05-20 | 2015-09-30 | 重庆大学 | A kind of synthetic method of ternary alkali metal-copper-chalcogmonocrystal monocrystal nano material |
| CN103601232B (en) * | 2013-09-18 | 2015-04-15 | 重庆大学 | Preparation method of KCu7S4 nano wire, and capacitor |
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| CN108675267B (en) * | 2018-06-14 | 2021-11-26 | 西南大学 | Universal method for preparing nano metal sulfide and compound thereof in one step |
| CN108906080B (en) * | 2018-07-11 | 2020-05-01 | 中国科学技术大学 | CdS/Cu2S/Co-based photoelectric catalytic material and preparation method thereof |
| CN112225256B (en) * | 2020-10-13 | 2022-11-22 | 湖北大学 | Preparation method of bismuth manganese sulfide nano material, super-hydrophobic sponge and preparation method and application of super-hydrophobic sponge |
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| CN1556028A (en) * | 2004-01-09 | 2004-12-22 | 中国科学院长春应用化学研究所 | Synthesis method of cadmium sulfide nano rod |
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| CN1556028A (en) * | 2004-01-09 | 2004-12-22 | 中国科学院长春应用化学研究所 | Synthesis method of cadmium sulfide nano rod |
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