CN101049918A - Method for preparing CdTe Nano grains possible to be dissolved in water and organic solvent - Google Patents
Method for preparing CdTe Nano grains possible to be dissolved in water and organic solvent Download PDFInfo
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- CN101049918A CN101049918A CN 200710099085 CN200710099085A CN101049918A CN 101049918 A CN101049918 A CN 101049918A CN 200710099085 CN200710099085 CN 200710099085 CN 200710099085 A CN200710099085 A CN 200710099085A CN 101049918 A CN101049918 A CN 101049918A
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Abstract
This invention discloses a method for preparing CdTe nanoparticles that can be dissolved in water and organic solvent. The method comprises: performing aqueous solution synthesis to prepare water-soluble CdTe nanocrystal, and modifying the surface of CdTe nanocrystal with linear alkylamine so that water-soluble CdTe nanocrystal is transferred into organic solvent. At the same time, adjusting the pH value of the aqueous solution can make CdTe nanocrystal redissolved in aqueous solution. The method can adjust the solubility of CdTe nanocrystal in aqueous solution and organic solvent by controlling the pH value of the aqueous solution as well as the concentration of alkylamine. The fluorescence quantum yield and half-peak width of CdTe nanocrystal dissolved in different solvents do not change largely. The method has such advantages as simple process and easy operation, and the obtained CdTe semiconductor nanocrystal can be used in biological probe and nanoparticle/polymer composite.
Description
Technical field
The invention belongs to the semiconductor nano material preparing technical field, relate to the preparation method of the CdTe semiconductor nanoparticle of a kind of water soluble and organic solvent, is to regulate by simple finishing and pH value, makes it can be dissolved in the aqueous solution and organic solvent.
Background technology
Semiconductor nanoparticle is because its unique quantum size effect and quantum confined effect, the CdTe nano particle is owing to have less energy gap, almost can cover whole visible region with its emmission spectrum of dimensional change, be widely used in fields such as photoelectronics, photodiode, solar cell, bioprobe.At present, the synthetic mainly synthetic and metal organic synthesis path of CdTe nano particle based on the aqueous solution.But, two kinds of methods respectively have relative merits, as document " Thiol-Capping of CdTe Nanocrystals:An Alternative to Organometallic Synthetic Routes ", Nikolai Gaponik, Dmitri V.Talapin, Andrey L.Rogach et al.J.Phys.Chem.B, 2002,106,7177-7185, systematically discussed the relative merits of two kinds of synthesis paths: metal is organic preparation method at high temperature carry out, and it is better to access crystal formation, narrow size distribution, and high nanocrystalline of fluorescence quantum efficiency.But the aerial unstable of product has limited their potential application; And water phase synthesis method is simple, low price, and environmental protection can be mass-produced, and can synthesize than littler nanocrystalline of organic method particle.
The most important thing is that the resulting CdTe nanocrystal surface of different synthetic methods has the group of opposed polarity, and it can only be existed in corresponding solvent, limited widely and used.By finishing, increase or change its surperficial group, can change the polarity of nano grain surface, make water miscible nanocrystalline being dissolved in the organic solvent; Same method can make oil-soluble nanocrystalline being dissolved in the aqueous solution.
Now, above-mentioned modifying method utilizes sulfhydryl compound to realize in nanocrystal surface by covalent coordinate.The sulfhydryl compound that will have long-chain is modified in the CdTe surface, make water miscible nanocrystalline being dissolved in the organic phase (see " Efficient Phase Transfer of Luminescent Thiol-Capped Nanocrystals:From Water to Nonpolar Organic Solvents " .Nikolai Gaponik, Dmitri V.Talapin, Andrey L.Rogach, et al.Nano Lett., 2 (8), 803-806).Equally, contain the sulfhydryl compound of hydrophilic radical (as carboxyl, amino etc.), also can modify, oil loving group is dissolved in the aqueous solution in nanocrystal surface.In addition, quaternary ammonium salt also often is used to modify in nanocrystal surface owing to have stronger electrostatic attraction ability, makes the nanocrystalline organic phase dissolved purpose that reaches in the aqueous solution.
Summary of the invention:
The present invention synthesizes water miscible CdTe nano particle with aqueous solution synthetic method, is coating materials with the hexadecylamine, can be with the nanocrystalline purpose that is dissolved in organic phase that reaches of water miscible CdTe.Simultaneously, by regulating pH value of aqueous solution, can shift the backwater phase again with the CdTe in the organic phase is nanocrystalline, thereby reach water-soluble purpose again.This method only needs simple operation, just can regulate the polarity of CdTe nanocrystal surface group arbitrarily, reaches the purpose of aqueous solution dissolving and organic solvent dissolution, has widened the nanocrystalline range of application in each field of CdTe.
The present invention includes following steps: 1, the water miscible CdTe semiconductor nano of preparation; 2, the finishing of chain alkyl amine makes it can be dissolved in organic solvent; 3, will be dissolved in that CdTe in the organic solvent is nanocrystalline to be dissolved in the aqueous solution again.
The invention provides the preparation method of the CdTe nano particle of a kind of water soluble and organic solvent, it is characterized in that, may further comprise the steps:
(1) with cadmium salt and mercaptan carboxylic acid's mixed aqueous solution, regulates pH to 11.2-11.8 with NaOH, at N
2Protection is down with tellurium source H
2Te feeds solution, obtains precursor solution, and wherein cadmium salt concentration is 2 * 10
-2Mol/L, cadmium salt, tellurium source, mercaptan carboxylic acid's mol ratio is 1: 0.5: 2.4, precursor solution obtains the CdTe nanocrystal solution at 100 ℃ of following backflow 15min-24h;
(2) the nanocrystalline aqueous solution of above-mentioned CdTe is regulated pH to 5-10 with NaOH, mix with the organic solvent that is dissolved with coating materials, the finishing agent concentration is 0.008-0.032mol/L, and after mixing solutions stirred, the CdTe that obtains being dissolved in organic solvent in organic solvent was nanocrystalline;
(3) pH value of water solution in the mixing solutions stirs back CdTe nano particle and is dissolved in the aqueous solution again to 11-14 in the usefulness NaOH regulating step (2).
Cadmium salt is CdCl
2, the mercaptan carboxylic acid is a Thiovanic acid.
Used coating materials is a hexadecylamine, and organic solvent is a chloroform, toluene.The finishing agent concentration is 0.016mol/L-0.032mol/L, and it is 5-8 that the nanocrystalline aqueous solution of above-mentioned CdTe is regulated pH with NaOH.
PH value of water solution during step (3) is regulated with NaOH in the mixing solutions is to 12-14.
The present invention is by aqueous solution synthetic method, and it is nanocrystalline to prepare the stable CdTe of the Thiovanic acid that can be dissolved in the aqueous solution.Utilize the weakly alkaline of straight chain alkyl amine, modify nanocrystal surface, it can be dissolved in the organic solvent in CdTe with the right form static of Louis's acid-alkali.The pH by regulating the aqueous solution and the concentration of alkylamine can be dissolved in (as shown in Figure 1) in the organic solvent the CdTe of difference amount is nanocrystalline.By regulating pH value in the aqueous solution, can be dissolved in the aqueous solution again the CdTe that is dissolved in organic solvent is nanocrystalline.Absorption spectrum and fluorescence spectrum show that the CdTe in the former aqueous solution is nanocrystalline, and considerable change does not take place for the CdTe of solution in organic solution nanocrystalline absorptive character and fluorescence property nanocrystalline and that be dissolved in the aqueous solution again.This method is simple to operate, can realize CdTe nanocrystalline in the aqueous solution and organic solvent dissolved regulate and control arbitrarily, make it at bioprobe, semi-conductor/organic polymer materials aspect has bigger using value.
Description of drawings:
Fig. 1 is to use solution that the present invention prepares in the nanocrystalline absorption spectrum of the CdTe of chloroformic solution.
Fig. 2 is that the CdTe of the aqueous solution for preparing of the present invention is nanocrystalline, is dissolved in the nanocrystalline fluorescence spectrum of CdTe that the CdTe of chloroformic solution is nanocrystalline and be dissolved in the aqueous solution again.
Embodiment:
Can better understand the present invention content by following representational embodiment and legend.
1: with CdCl
2, H
2Te, Thiovanic acid are that the water miscible CdTe of feedstock production is nanocrystalline
With 228.4mg CdCl
22.5H
2O is dissolved in the 50ml water, stirs down dropwise to add the 0.16ml Thiovanic acid, regulates pH to 11.2 with 1mol/L NaOH, logical N
2, stir down H
2Te is fed in the solution by nitrogen, and gained solution is 100 ℃ of backflows, and the CdTe that gets the varying particle size size is nanocrystalline.Heating 5h solution absorption is shown in Fig. 1 curve 1, and fluorogram is shown in Fig. 2 curve 1.
2: CdTe is nanocrystalline for alkylamine prepared by surface modification chloroformic solution dissolved
Get a 4ml heating 5h solution 4ml set by step, regulate pH=6, mix with the 4ml chloroformic solution that is dissolved with the 30.8mg hexadecylamine, stir, CdTe is nanocrystalline to be dissolved in the chloroformic solution gradually.Leave standstill behind the 2h, the solution layering records chloroform and absorbs mutually shown in Fig. 1 curve 2, and fluorogram is shown in Fig. 2 curve 2.
The nanocrystalline aqueous solution that is dissolved in again of 3:CdTe.
Water layer pH value of solution=11 in the regulating step 2 continue to stir, and CdTe is nanocrystalline to be dissolved in the aqueous solution gradually again.Leave standstill the solution layering.Aqueous solution fluorogram is shown in Fig. 2 curve 3.
Quantum yield and peak width at half height that above steps gained CdTe is nanocrystalline are listed in table one.
The nanocrystalline synthetic method of 1:CdTe is as described in the embodiment 1.
2: CdTe is nanocrystalline for alkylamine prepared by surface modification chloroformic solution dissolved
Get a 4ml heating 5h solution 4ml set by step, regulate pH=5, mix with the 4ml chloroformic solution that is dissolved with the 15.4mg hexadecylamine, stir, CdTe is nanocrystalline to be dissolved in the chloroformic solution gradually.Leave standstill behind the 2h, the solution layering records chloroform and absorbs mutually shown in Fig. 1 curve 3.
The nanocrystalline aqueous solution that is dissolved in again of 3:CdTe is shown in embodiment 1.
The nanocrystalline synthetic method of 1:CdTe is as described in the embodiment 1.
2: CdTe is nanocrystalline for alkylamine prepared by surface modification chloroformic solution dissolved
Get a 4ml heating 5h solution 4ml set by step, regulate pH=6, mix with the 4ml chloroformic solution that is dissolved with the 7.7mg hexadecylamine, stir, CdTe is nanocrystalline to be dissolved in the chloroformic solution gradually.Leave standstill behind the 2h, the solution layering records chloroform and absorbs mutually shown in Fig. 1 curve 4.
The nanocrystalline aqueous solution that is dissolved in again of 3:CdTe is shown in embodiment 1.
Embodiment 4
The nanocrystalline synthetic method of 1:CdTe is as described in the embodiment 1.
2: CdTe is nanocrystalline for alkylamine prepared by surface modification chloroformic solution dissolved
Get a 4ml heating 1h solution 4ml set by step, regulate pH=8, mix with the 4ml chloroformic solution that is dissolved with the 30.8mg hexadecylamine, stir, CdTe is nanocrystalline to be dissolved in the chloroformic solution gradually.Leave standstill the solution layering behind the 2h.
3: water layer pH value of solution=14 in the regulating step 2, continue to stir, CdTe is nanocrystalline to be dissolved in the aqueous solution gradually again.Leave standstill the solution layering.
Quantum yield and peak width at half height that above steps gained CdTe is nanocrystalline are listed in table one.
Embodiment 5
The nanocrystalline synthetic method of 1:CdTe is as described in the embodiment 1.
2: CdTe is nanocrystalline for alkylamine prepared by surface modification chloroformic solution dissolved
Get a 4ml heating 15min solution 4ml set by step, regulate pH=6, mix with the 4ml chloroformic solution that is dissolved with the 30.8mg hexadecylamine, stir, CdTe is nanocrystalline to be dissolved in the chloroformic solution gradually.Leave standstill the solution layering behind the 2h.
The nanocrystalline aqueous solution that is dissolved in again of 3:CdTe is shown in embodiment 1.
Embodiment 6
The nanocrystalline synthetic method of 1:CdTe is as described in the embodiment 1.
2: alkylamine prepared by surface modification chloroformic solution dissolved CdTe is nanocrystalline as described in the embodiment 1.
The nanocrystalline aqueous solution that is dissolved in again of 3:CdTe.
Water layer pH value of solution=14 in the regulating step 2 continue to stir, and CdTe is nanocrystalline to be dissolved in the aqueous solution gradually again.
Quantum yield and peak width at half height that above steps gained CdTe is nanocrystalline are listed in table one.
Table one
| Embodiment | The former aqueous solution | Chloroformic solution | Again be dissolved in the aqueous solution | |||
| Quantum yield (%) | Peak width at half height (nm) | Quantum yield (%) | Peak width at half height (nm) | Quantum yield (%) | Peak width at half height (nm) | |
| 1 | 15.8 | 43.7 | 19.4 | 45.5 | 15.0 | 44.5 |
| 4 | 10.8 | 41.8 | 14.4 | 42.2 | 11.9 | 41.5 |
| 5 | 5.2 | 37.9 | 9.8 | 37.6 | 5.5 | 38.1 |
Claims (5)
1, the preparation method of the CdTe nano particle of a kind of water soluble and organic solvent is characterized in that, may further comprise the steps:
(1) with cadmium salt and mercaptan carboxylic acid's mixed aqueous solution, regulates pH to 11.2-11.8 with NaOH, at N
2Protection is down with tellurium source H
2Te feeds solution, obtains precursor solution, and wherein cadmium salt concentration is 2 * 10
-2Mol/L, cadmium salt, tellurium source, mercaptan carboxylic acid's mol ratio is 1: 0.5: 2.4, precursor solution obtains the CdTe nanocrystal solution at 100 ℃ of following backflow 15min-24h;
(2) the nanocrystalline aqueous solution of above-mentioned CdTe is regulated pH to 5-10 with NaOH, mix with the organic solvent that is dissolved with coating materials, the finishing agent concentration is 0.008-0.032mol/L, and after mixing solutions stirred, the CdTe that obtains being dissolved in organic solvent in organic solvent was nanocrystalline;
(3) pH value of water solution in the mixing solutions stirs back CdTe nano particle and is dissolved in the aqueous solution again to 11-14 in the usefulness NaOH regulating step (2).
2, the preparation method of the CdTe nano particle of water soluble as claimed in claim 1 and organic solvent is characterized in that: cadmium salt is CdCl
2, the mercaptan carboxylic acid is a Thiovanic acid.
3, the preparation method of the CdTe nano particle of water soluble as claimed in claim 1 and organic solvent is characterized in that: used coating materials is a hexadecylamine, and organic solvent is a chloroform, toluene.
4, the preparation method of the CdTe nano particle of water soluble as claimed in claim 1 and organic solvent is characterized in that: the finishing agent concentration is 0.016mol/L-0.032mol/L, and it is 5-8 that the nanocrystalline aqueous solution of above-mentioned CdTe is regulated pH with NaOH.
5, the preparation method that can be dissolved in the CdTe nano particle of the aqueous solution and organic solvent as claimed in claim 1 is characterized in that, the pH value of water solution during step (3) is regulated with NaOH in the mixing solutions is to 12-14.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101431148B (en) * | 2008-10-13 | 2010-06-02 | 同济大学 | Method for improving illumination intensity of CdTe nano compound film |
| CN101603085B (en) * | 2009-07-07 | 2011-11-09 | 天津工业大学 | Magnetic DNA fluorescent probe and preparation method thereof |
| CN102554217A (en) * | 2012-02-24 | 2012-07-11 | 河南大学 | Water-soluble nano-copper and preparation method thereof |
| CN102703082A (en) * | 2012-05-09 | 2012-10-03 | 北京化工大学 | Preparation method of water-soluble CdTe nanometer particles with high fluorescence property |
| CN103274371A (en) * | 2013-06-07 | 2013-09-04 | 吉林大学 | Method for preparing oil-soluble telluride semiconductor nano-crystal by adopting alkyl amide as solvent |
| CN107315091A (en) * | 2017-06-29 | 2017-11-03 | 重庆师范大学 | One kind detection Cistofuran metabolite quantum dot immune chromatographic test paper, preparation method and applications |
| CN115465842A (en) * | 2022-09-02 | 2022-12-13 | 江西铜业股份有限公司 | 4N tellurium casting method |
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2007
- 2007-05-11 CN CN2007100990853A patent/CN101049918B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101431148B (en) * | 2008-10-13 | 2010-06-02 | 同济大学 | Method for improving illumination intensity of CdTe nano compound film |
| CN101603085B (en) * | 2009-07-07 | 2011-11-09 | 天津工业大学 | Magnetic DNA fluorescent probe and preparation method thereof |
| CN102554217A (en) * | 2012-02-24 | 2012-07-11 | 河南大学 | Water-soluble nano-copper and preparation method thereof |
| CN102554217B (en) * | 2012-02-24 | 2014-12-17 | 河南大学 | Water-soluble nano-copper and preparation method thereof |
| CN102703082A (en) * | 2012-05-09 | 2012-10-03 | 北京化工大学 | Preparation method of water-soluble CdTe nanometer particles with high fluorescence property |
| CN102703082B (en) * | 2012-05-09 | 2014-01-01 | 北京化工大学 | Preparation method of water-soluble CdTe nanometer particles with high fluorescence property |
| CN103274371A (en) * | 2013-06-07 | 2013-09-04 | 吉林大学 | Method for preparing oil-soluble telluride semiconductor nano-crystal by adopting alkyl amide as solvent |
| CN107315091A (en) * | 2017-06-29 | 2017-11-03 | 重庆师范大学 | One kind detection Cistofuran metabolite quantum dot immune chromatographic test paper, preparation method and applications |
| CN115465842A (en) * | 2022-09-02 | 2022-12-13 | 江西铜业股份有限公司 | 4N tellurium casting method |
| CN115465842B (en) * | 2022-09-02 | 2024-03-08 | 江西铜业股份有限公司 | 4N tellurium casting method |
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