CN101844801B - A kind of monodisperse water-soluble lead sulfide nanocrystal cluster and preparation method thereof - Google Patents
A kind of monodisperse water-soluble lead sulfide nanocrystal cluster and preparation method thereof Download PDFInfo
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- 229910052981 lead sulfide Inorganic materials 0.000 title abstract description 14
- 239000002159 nanocrystal Substances 0.000 title abstract 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 52
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 20
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 50
- 239000011541 reaction mixture Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 6
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
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- 238000001514 detection method Methods 0.000 abstract 1
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- -1 Wang and for example Chemical compound 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
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- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
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- 239000002071 nanotube Substances 0.000 description 1
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明的一种单分散水溶性硫化铅纳米晶簇及其制备方法属于溶液化学方法合成技术。硫化铅纳米晶簇呈球形，由多个纳米晶组成。制备方法是将醋酸铅、聚丙烯酸和一缩二乙二醇按照一定的比例混合，在氮气保护下搅拌加热，快速的注入硫脲的一缩二乙二醇溶液，恒定反应温度在210℃左右，反应5～30分钟，将反应产物冷却，反复用水和乙醇洗涤再真空干燥，制得单分散水溶性硫化铅纳米晶簇。本发明所得到的单分散硫化铅胶体纳米晶簇具有很好的水溶性，尺寸可以调控且粒子在可见光和近红外区有吸收；原料廉价易得，工艺简单，成本低，工艺重复性好；在近红外探测、光子开关和太阳能电池等方面有着广阔的应用前景。
The invention discloses a monodisperse water-soluble lead sulfide nano crystal cluster and a preparation method thereof, which belong to the synthesis technology of solution chemical method. The lead sulfide nanocrystal clusters are spherical and consist of multiple nanocrystals. The preparation method is to mix lead acetate, polyacrylic acid and diethylene glycol according to a certain ratio, stir and heat under the protection of nitrogen, and quickly inject the diethylene glycol solution of thiourea. The constant reaction temperature is about 210°C. After reacting for 5-30 minutes, the reaction product is cooled, repeatedly washed with water and ethanol, and vacuum-dried to prepare monodisperse water-soluble lead sulfide nano crystal clusters. The monodisperse lead sulfide colloidal nanocrystal clusters obtained by the present invention have good water solubility, the size can be adjusted, and the particles have absorption in the visible light and near-infrared regions; the raw materials are cheap and easy to obtain, the process is simple, the cost is low, and the process repeatability is good; It has broad application prospects in near-infrared detection, photon switches and solar cells.
Description
Technical field
The invention belongs to the solution chemical processes synthetic technology, particularly relate to a kind of preparation method of lead sulfide colloidal nano druse.
Background technology
Lead sulfide (PbS) is a kind of important semiconductor material in the IV-VI family, has very narrow band gap (0.41eV) and big bohr exciton radius (18nm), and this just makes its quantum confined effect more obvious.The PbS of nanoscale can be with can regulate and control between near infrared and visible region and move, its cubic non-linearity optic response is expected to reach the thirtyfold of GaAs, 1,000 times of CdSe, at infrared acquisition [CN2217221], solar cell, photon switch and aspects such as heat and bio-imaging important use is arranged, therefore also become pursuing one's goal of numerous researchers.In various Application Areass, the particularly preparation of new forms of energy and utilization and device preparation etc., the particle that all requires us to prepare has good dispersiveness in solvent, and considers preferably can be distributed to particularly aqueous phase of green solvent commonly used from environment and cost angle.Therefore, the preparation of water-soluble colloid particle is the important directions of present colloidal particle preparation.
The preparation process of lead sulfide semiconductor nano material mainly comprises physics and two kinds of methods of chemistry at present.Wherein particularly noticeable to the research of chemical process especially liquid-phase system synthetic method (claiming wet chemistry method again) in recent years.Its reason is the go out color control of this method to particle morphology, composition, operates simply relatively, is easy to amplify plurality of advantages such as preparation and good compatibility and is widely accepted by everybody.Research for lead sulfide at present mainly is divided into two aspects, be synthetic high-quality sulfide nanocrystalline on the one hand, mainly be that to select organic molecules such as organic amine, organic acid, organic phosphine for use be the finishing molecule, in the organic reaction medium, obtain having the lead sulfide quantum dot of certain size and pattern by high-temperature heating process.Adopting the non-ligand solvent liquid-phase system of octadecene as people such as Warner [Adv.Mater.2008,20,784], is that the synthetic PbS of raw material is nanocrystalline with plumbic acetate and sulphur powder.The subject matter that this method exists is to be reflected in the organic medium to carry out, and brings problems such as solvent recuperation utilization; Nanocrystalline can only being distributed in the non-polar solvent has great limitation for its application simultaneously.Be lead sulfide nano material [CN1594100 on the other hand by synthetic different-shape under the condition that exists at different tensio-active agents, CN101497784, CN101117237, CN101402467], [J.Phys.Chem.B2006 such as Wang and for example, 110,184] adopt solvent-thermal method to prepare the PbS nanotube; [J.Phys.Chem.B2006,110,6543] such as L ü adopt circumfluence method to prepare the PbS nano material of various different-shapes.But because resulting scantling is considerably beyond its exciton Bohr radius (18nm), quantum confined effect can't embody, and potential is used still the great limitation effect.
Summary of the invention
The objective of the invention is at the deficiency that exists in the background technology, the chemical preparation process of a kind of single dispersion, highly water-soluble lead sulfide colloidal nano druse is provided.Can solve among the existing preparation method problem that the particle that far surpasses the exciton Bohr radius for size can't produce quantum confined effect, is difficult to realize aspect existence such as single dispersions in water.
Monodisperse water soluble sulfide nanocrystalline of the present invention is bunch spherical in shape, diameter is 150～240nm, each sulfide nanocrystalline is bunch by a plurality of nanocrystalline compositions, and promptly sulfide nanocrystalline bunch is assembled by sulfide nanocrystalline and to be formed, and each sulfide nanocrystalline granularity is 6～8nm.
Polyacrylic acid is present on the sulfide nanocrystalline bunch; Polyacrylic carboxyl is connected by electrostatic interaction with lead ion.
The method for preparing monodisperse water soluble sulfide nanocrystalline bunch of the present invention is plumbous source with plumbic acetate, is the sulphur source with the thiocarbamide, is the finishing macromole with the polyacrylic acid, and glycol ether (DEG) is a solvent, reacts under nitrogen protection.Concrete steps are as follows:
1. the ratio of thiocarbamide and DEG 1: 25 in molar ratio～27 three mouthfuls of round-bottomed flasks in mix, mixture to clarification, obtains the glycol ether solution (temperature during stirring does not have big influence 100 ± 20 ℃ of scopes to the producing of glycol ether solution of thiocarbamide) of thiocarbamide 80～120 ℃ of heated and stirred;
2. plumbic acetate, DEG and polyacrylic acid 1: 200 in molar ratio～220: 15～20 mixed in three mouthfuls of round-bottomed flasks, obtain reaction mixture;
3. with reaction mixture heated and stirred under nitrogen protection, when the temperature of reaction mixture is elevated to 200～220 ℃, inject the glycol ether solution of thiocarbamide; Constant in then 200～220 ℃ of thermotonuses 5～30 minutes, be cooled to normal temperature; The consumption of the glycol ether solution of thiocarbamide is 0.5～2.0: 1 calculating by the mol ratio of thiocarbamide and plumbic acetate;
4. reaction product is added behind the ethanol centrifugally, precipitation water and washing with alcohol are removed DEG and unreacted polyacrylic acid in the dereaction, and vacuum-drying again makes monodisperse water soluble sulfide nanocrystalline bunch.
In the preparation process of above-mentioned sulfide nanocrystalline bunch, the consumption of solvent DEG in the certain volume scope to almost not influence of the finished product, the number of times of the repetitive scrubbing when only influencing aftertreatment.
Advantage and effect: the hot injection method of the present invention by simple controllable, select for use polyacrylic acid to do the finishing macromole and prepare single the dispersion and the sulfide nanocrystalline of highly water-soluble bunch.Method raw material of the present invention is cheap and easy to get, and technology is simple, and cost is low, is easy to control and good process repeatability.By infrared spectrum characterization washing dried sulfide nanocrystalline bunch, proved that polyacrylic acid is present in sulfide nanocrystalline and bunch goes up (referring to Fig. 4).Carboxyl in the polyacrylic acid and lead ion have very strong coordination, have neither part nor lot in coordinate carboxyl negative ion and stretch into then that to make in the aqueous solution that sulfide nanocrystalline bunch demonstrates well water-soluble.Two step of reaction have been experienced in the formation of sulfide nanocrystalline bunch: sulfide nanocrystalline nucleation (fs) in supersaturated solution at first, these nanocrystalline reunions in order to reduce self great surface energy generate nanometer crystal druse (subordinate phase) then.The existence of this secondary structure makes sulfide nanocrystalline that the existence of quantum confinement effect bunch still be arranged, and therefore at visible light and near-infrared region tangible absorption (referring to Fig. 3) is arranged still.This has just overcome the defective that synthetic large size particle does not in the past have quantum confinement effect, has remedied quantum dot again because the deficiency that self minimum size is difficult for controlling has very big realistic meaning and a wide application prospect.
Description of drawings
Fig. 1 is the XRD figure of the monodispersed sulfide nanocrystalline of different size of the present invention bunch.
The XRD figure of (a) sulfide nanocrystalline of making for embodiment 1 bunch wherein;
(b) XRD figure of the sulfide nanocrystalline that makes for embodiment 2 bunch;
(c) XRD figure of the sulfide nanocrystalline that makes for embodiment 3 bunch.
Fig. 2 is transmission electron microscope (TEM) photo and the distribution of sizes of the monodispersed sulfide nanocrystalline of different size of the present invention bunch.
The wherein transmission electron microscope and the corresponding distribution of sizes of (a) sulfide nanocrystalline of making for embodiment 1 bunch;
(b) transmission electron microscope of the sulfide nanocrystalline that makes for embodiment 2 bunch and corresponding distribution of sizes;
(c) transmission electron microscope of the sulfide nanocrystalline that makes for embodiment 3 bunch and corresponding distribution of sizes.
Fig. 3 is the monodispersed sulfide nanocrystalline of the present invention bunch absorption spectrum in the near-infrared region.
The absorption spectrum of (a) sulfide nanocrystalline of making for embodiment 1 bunch wherein;
(b) absorption spectrum of the sulfide nanocrystalline that makes for embodiment 2 bunch;
(c) absorption spectrum of the sulfide nanocrystalline that makes for embodiment 3 bunch.
Fig. 4 is the infrared absorption spectrum of the monodispersed sulfide nanocrystalline of the present invention bunch.
(a) protonated polyacrylic infrared absorption spectrum wherein;
(b) infrared absorption spectrum of the sulfide nanocrystalline tied up of polyacrylate bag bunch;
The infrared absorption spectrum of the sulfide nanocrystalline that the polyacrylic acid bag after (c) protonated is tied up bunch.
Embodiment
Be described further below by the preparation of specific embodiment to monodisperse water soluble sulfide nanocrystalline among the present invention bunch, its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention.
Embodiment 1
With 8 * 10
-3Mol analytical pure thiocarbamide mixes in three mouthfuls of round-bottomed flasks of 100ml with 20 milliliters of analytical pure glycol ethers (DEG), and mixture obtains thiocarbamide/DEG solution 100 ℃ of heated and stirred one hour.
With 0.4 * 10
-3Mol analytical pure plumbic acetate, 6.0 * 10
-3Mol analytical pure polyacrylic acid, 8 milliliters of analytical pure DEG mix in three mouthfuls of round-bottomed flasks of 50ml, and reaction mixture is heated and stirred under nitrogen protection.
When the temperature of reaction mixture is elevated to 215 ℃, inject thiocarbamide/DEG solution of 1.0 milliliters fast after, constant temperature of reaction is at 210 ℃, the reaction times is 11 minutes, is cooled to normal temperature.
Reaction product adds behind the ethanol centrifugal, and precipitation water and ethanol repetitive scrubbing remove DEG and unreacted unnecessary polyacrylic acid in the dereaction, carry out vacuum-drying then, can prepare the sulfide nanocrystalline bunch of monodisperse water soluble.
Product is accredited as lead sulfide (in as Fig. 1 a) through X-ray powder diffraction; Transmission electron microscope (TEM) detect the product pattern (as among Fig. 2 a), the diameter Distribution of sulfide nanocrystalline bunch is narrower, is about 150～155nm.
Embodiment 2
With 8 * 10
-3Mol analytical pure thiocarbamide mixes in three mouthfuls of round-bottomed flasks of 100ml with 20 milliliters of analytical pure glycol ethers (DEG), and mixture obtains thiocarbamide/DEG solution 100 ℃ of heated and stirred one hour.
With 0.4 * 10
-3Mol analytical pure plumbic acetate, 6.0 * 10
-3Mol analytical pure polyacrylic acid, 8 milliliters of analytical pure DEG mix in three mouthfuls of round-bottomed flasks of 50ml, and reaction mixture is heated and stirred under nitrogen protection.
When the temperature of reaction mixture is elevated to 215 ℃, inject thiocarbamide/DEG solution of 1.5 milliliters fast after, constant temperature of reaction is at 210 ℃, the reaction times is 11 minutes, is cooled to normal temperature.
Reaction product adds behind the ethanol centrifugal, and precipitation water and ethanol repetitive scrubbing remove DEG and unreacted unnecessary polyacrylic acid in the dereaction, carry out vacuum-drying then, can prepare the sulfide nanocrystalline bunch of monodisperse water soluble.
Product is accredited as lead sulfide (b in as Fig. 1) through X-ray powder diffraction; Transmission electron microscope (TEM) detects product pattern (as b among Fig. 2), and the diameter Distribution of sulfide nanocrystalline bunch is narrower, is about 180～190nm.
Embodiment 3
With 8 * 10
-3Mol analytical pure thiocarbamide mixes in three mouthfuls of round-bottomed flasks of 100ml with 20 milliliters of analytical pure glycol ethers (DEG), and mixture obtains thiocarbamide/DEG solution 100 ℃ of heated and stirred one hour.
With 0.4 * 10
-3Mol analytical pure plumbic acetate, 6.0 * 10
-3Mol analytical pure polyacrylic acid, 8 milliliters of analytical pure DEG mix in three mouthfuls of round-bottomed flasks of 50ml, and reaction mixture is heated and stirred under nitrogen protection.
When the temperature of reaction mixture is elevated to 215 ℃, inject thiocarbamide/DEG solution of 2.0 milliliters fast after, constant temperature of reaction is at 210 ℃, the reaction times is 11 minutes, is cooled to normal temperature.
Reaction product adds behind the ethanol centrifugal, and precipitation water and ethanol repetitive scrubbing remove DEG and unreacted unnecessary polyacrylic acid in the dereaction, carry out vacuum-drying then, can prepare the sulfide nanocrystalline bunch of monodisperse water soluble.
Product is accredited as lead sulfide (c in as Fig. 1) through X-ray powder diffraction; Transmission electron microscope (TEM) detects product pattern (as c among Fig. 2), and the diameter Distribution of sulfide nanocrystalline bunch is narrower, is about 220～240nm.
Embodiment 4
With 8 * 10
-3Mol analytical pure thiocarbamide mixes in three mouthfuls of round-bottomed flasks of 100ml with 20 milliliters of analytical pure DEG, and mixture obtains thiocarbamide/DEG solution 100 ℃ of heated and stirred one hour.
With 0.4 * 10
-3Mol analytical pure plumbic acetate, 8.0 * 10
-3Mol analytical pure polyacrylic acid, 8 milliliters of analytical pure DEG mix in three mouthfuls of round-bottomed flasks of 50ml, and reaction mixture is heated and stirred under nitrogen protection.
When the temperature of reaction mixture is elevated to 220 ℃, inject thiocarbamide/DEG solution of 0.5 milliliter fast after, constant temperature of reaction is at 210 ℃, the reaction times is 6 minutes, is cooled to normal temperature.
Reaction product adds behind the ethanol centrifugal, and precipitation water and ethanol repetitive scrubbing remove DEG and unreacted unnecessary polyacrylic acid in the dereaction, carry out vacuum-drying then, can prepare the sulfide nanocrystalline bunch of monodisperse water soluble.
In embodiment 1～4, in reaction mixture, inject thiocarbamide/DEG solution after, constant temperature of reaction is at 200～220 ℃, the reaction times is at 5～30 minutes, all can prepare the sulfide nanocrystalline bunch of monodisperse water soluble.
Claims (2)
1. a monodisperse water soluble sulfide nanocrystalline bunch is characterized in that, sulfide nanocrystalline is bunch spherical in shape, and diameter is 150～240nm; Sulfide nanocrystalline bunch is assembled by sulfide nanocrystalline and is formed, and each sulfide nanocrystalline granularity is 6～8nm; Polyacrylic acid is present on the sulfide nanocrystalline bunch, and polyacrylic carboxyl is connected by electrostatic interaction with lead ion.
2. the preparation method of the monodisperse water soluble sulfide nanocrystalline of a claim 1 bunch, step is as follows:
1. thiocarbamide is mixed in three mouthfuls of round-bottomed flasks with the ratio of glycol ether 1: 25 in molar ratio～27, mixture to clarification, obtains the glycol ether solution of thiocarbamide 80～120 ℃ of heated and stirred;
2. plumbic acetate, glycol ether and polyacrylic acid 1: 200 in molar ratio～220: 15～20 mixed in three mouthfuls of round-bottomed flasks, obtain reaction mixture;
3. with reaction mixture heated and stirred under nitrogen protection, when the temperature of reaction mixture is elevated to 200～220 ℃, inject the glycol ether solution of thiocarbamide; Constant in then 200～220 ℃ of thermotonuses 5～30 minutes, be cooled to normal temperature; The consumption of the glycol ether solution of thiocarbamide is 0.5～2.0: 1 calculating by the mol ratio of thiocarbamide and plumbic acetate;
4. reaction product is added behind the ethanol centrifugally, precipitation water and washing with alcohol are removed glycol ether and unreacted polyacrylic acid in the dereaction, and vacuum-drying again makes monodisperse water soluble sulfide nanocrystalline bunch.
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| CN101844801A (en) | 2010-09-29 |
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