CN111378433A - Quantum dot ligand exchange method - Google Patents
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- CN111378433A CN111378433A CN201811643017.3A CN201811643017A CN111378433A CN 111378433 A CN111378433 A CN 111378433A CN 201811643017 A CN201811643017 A CN 201811643017A CN 111378433 A CN111378433 A CN 111378433A
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
Abstract
The invention discloses a quantum dot ligand exchange method, which comprises the steps of mixing a complex molecule generated by mixing mercaptocarboxylic acid and organic amine with a quantum dot, and carrying out exchange reaction on the complex molecule and a ligand on the surface of the quantum dot to obtain a quantum dot solution with the surface combined with the complex molecule; and mixing the quantum dots with the surface combined with the complexing molecules with a polar solvent and carrying out heat treatment to obtain the water-soluble quantum dots with the surface combined with the mercapto carboxylic acid. The invention can realize the complete exchange of the ligands on the surface of the quantum dot, thereby reducing the defects on the surface of the quantum dot.
Description
Technical Field
The invention relates to the field of quantum dots, in particular to a quantum dot ligand exchange method.
Background
The quantum dot nanocrystal is an important nano material, and relates to the wide application range of quantum dot nano, such as: light emitting diodes, batteries, biology, display, lighting, etc.
Quantum dots applied to light emitting and battery devices use surface treatment techniques such as ligand exchange for quantum dots. The conventional ligand exchange is to exchange another ligand on the surface of the oil-soluble quantum dot by using a short-chain ligand to prepare the water-soluble quantum dot; in the process of exchanging ligands on the surface of the oil-soluble quantum dot by using ligands with shorter chain length and containing carboxyl or sulfydryl, the quantum dot with incomplete surface ligand exchange is usually obtained, so that the corresponding defects exist on the surface of the quantum dot.
Therefore, the prior art is still to be improved.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a quantum dot ligand exchange method, which aims to solve the problem that the existing quantum dot has defects on the surface of the quantum dot due to incomplete ligand exchange when ligand exchange is carried out.
The technical scheme of the invention is as follows:
mixing mercaptocarboxylic acid and organic amine to generate a complex molecule;
mixing the complexing molecules with quantum dots to perform an exchange reaction between the complexing molecules and ligands on the surfaces of the quantum dots to obtain the quantum dots with the complexing molecules bound on the surfaces;
and mixing the quantum dots with the surface combined with the complexing molecules with a polar solvent to obtain the quantum dots with the surface combined with the mercapto carboxylic acid.
Has the advantages that: the invention provides a quantum dot ligand exchange method, which comprises the steps of mixing a complex molecule generated by mixing mercaptocarboxylic acid and organic amine with a quantum dot, and carrying out exchange reaction on the complex molecule and a ligand on the surface of the quantum dot to obtain the quantum dot with the surface combined with the complex molecule; and mixing the quantum dots with the surface combined with the complexing molecules with a polar solvent and carrying out heat treatment to obtain the quantum dots with the surface combined with the mercapto carboxylic acid. The invention can realize the complete exchange of the ligands on the surface of the quantum dot, thereby reducing the defects on the surface of the quantum dot.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of a quantum dot ligand exchange method of the present invention.
Detailed Description
The invention provides a quantum dot ligand exchange method, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the present invention provides a flow chart of a preferred embodiment of a quantum dot ligand exchange method, wherein, as shown in the figure, the method comprises the following steps:
s100, mixing mercaptocarboxylic acid and organic amine to generate a complex molecule;
s200, mixing the complexing molecules with the quantum dots to perform an exchange reaction between the complexing molecules and ligands on the surfaces of the quantum dots to obtain the quantum dots with the surface bound with the complexing molecules;
and S300, mixing the quantum dots with the surface combined with the complexing molecules with a polar solvent to obtain the quantum dots with the surface combined with the mercapto carboxylic acid.
The quantum dot ligand exchange method provided by the embodiment can realize complete exchange of the quantum dot surface ligands, so that the defects on the quantum dot surface are reduced. The mechanism for achieving the above effects is specifically as follows:
in the process of mixing the mercapto carboxylic acid and the organic amine, the carboxyl functional group (-COOH) on the mercapto carboxylic acid is easy to remove H under the condition of predetermined temperature+form-COO-And amino functions (-NH) on organic amines2) H is easily obtained under the condition of predetermined temperature+Formation of-NH3 +The group-COO-and-NH3 +The complex molecules are adsorbed together through electrostatic interaction to form complex molecules, the chain length of the complex molecules is long, the complex molecules have strong non-polarity, and ligand exchange reaction can be fully generated after the complex molecules are mixed with quantum dots to obtain the quantum dots with the surface combined with the complex molecules; further, the quantum dots with the surface combined with the complexing molecules are mixed with a polar solvent, so that carboxylate ions and ammonium ions in the complexing molecules combined with the surfaces of the quantum dots can be separated, and the quantum dots with the surface combined with the mercapto carboxylic acid can be obtained. The quantum dot ligand exchange method provided by the embodiment can effectively improve the quality of quantum dot ligand exchange and reduce the surface defects after quantum dot ligand exchange.
In a preferred embodiment, the mercaptocarboxylic acid is a linear organic molecule having one mercapto group and one carboxyl group and having the general chemical structure HS- (CH)2)n-COOH, wherein n is an integer of 1 or more and 11 or less. By way of example, the mercaptocarboxylic acid may be selected from one or more of thioglycolic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptopentanoic acid, mercaptohexanoic acid, mercaptoheptanoic acid, mercaptooctanoic acid, mercaptononanoic acid, mercaptodecanoic acid, and mercaptoundecanoic acid.
Preferably, the organic amine is a linear organic molecule containing only one amino functional group, and the chemical structure general formula is CH3- (CH2)m-NH2Wherein m is an integer of 7 or more and 17 or less. By way of example, the organic amine may be selected from one or more of oleylamine, octylamine, octadecylamine, tetradecylamine, dodecylamine, and hexadecylamine, but is not limited thereto.
In a preferred embodiment, the mercaptocarboxylic acid and the organic amine are mixed at a first temperature of 30 to 100 ℃ such that the carboxylate ions in the mercaptocarboxylic acid combine with the ammonium ions in the organic amine to form the complex molecule. In this embodiment, the mercapto carboxylic acid is a water-soluble molecule, the organic amine is an oil-soluble molecule, and a complex molecule generated by a reaction between the mercapto carboxylic acid and the organic amine is a nonpolar molecule and has a mercapto functional group, so that the complex molecule can sufficiently perform an exchange reaction with a ligand on the surface of the quantum dot.
In a preferred embodiment, the mercaptocarboxylic acid and the organic amine are mixed in a molar weight ratio of mercaptocarboxylic acid to organic amine of from 1:1 to 2. In a preferred embodiment, the carboxylate ions in the mercaptocarboxylic acid are combined with the ammonium ions in the organic amine under heating conditions of 30 to 100 ℃ to form the complex molecule.
In a preferred embodiment, the mass ratio of the molar weight of the complexing molecule to the oil-soluble quantum dot is 1-10 mmol: 100mg, mixing the complexing molecule with the quantum dots. In a preferred embodiment, the complexing molecule and the quantum dot are mixed under the temperature condition of 60-200 ℃, and the complexing molecule and the ligand on the surface of the quantum dot are subjected to an exchange reaction to obtain the quantum dot with the surface bound with the complexing molecule.
In this embodiment, since the complexing molecules are nonpolar molecules, the quantum dots can be sufficiently dispersed in the complexing molecules under heating conditions, so that the ligand exchange reaction is sufficiently performed, and the quantum dot solution with the complexing molecules bound on the surface is obtained.
Preferably, the quantum dots are selected from one or more of binary phase quantum dots, ternary phase quantum dots and quaternary phase quantum dots, but not limited thereto. By way of example, the binary phase quantum dots include, but are not limited to, CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS, and the like; the ternary phase quantum dots include, but are not limited to, ZnCdS, CuInS, ZnCdSe, ZnSeS, ZnCdTe, PbSeS, etc.; the quaternary phase quantum dots include ZnCdS/ZnSe, CuInS/ZnS, ZnCdSe/ZnS, CuInSeS, ZnCdTe/ZnS, PbSeS/ZnS, etc., but are not limited thereto. More preferably, the ligand on the surface of the quantum dot is selected from one or more of oleic acid, oleylamine, octylamine, trioctylphosphine, octadecylphosphine and tetradecylphosphine, but is not limited thereto.
In a preferred embodiment, the quantum dots with the complexing molecules bound to the surfaces are mixed with a polar solvent at a third temperature of 30-100 ℃ to separate carboxylate ions and ammonium ions in the complexing molecules bound to the surfaces of the quantum dots, so as to obtain the quantum dots with the mercapto carboxylic acid bound to the surfaces.
In this embodiment, through stirring the quantum dot solution that is combined with the complexing molecule and heat the processing, can make carboxylate radical ion and ammonium ion in the complexing molecule of quantum dot surface bonding separate, obtain the quantum dot that surface bonding has the mercapto carboxylic acid, in the stirring process, the water-soluble quantum dot that is combined with the mercapto carboxylic acid can disperse in the polar solvent, can obtain the quantum dot that the surface bonding has the mercapto carboxylic acid of purification after adding extractant and carrying out centrifugal separation.
Preferably, the polar solvent is selected from one or more of methanol, ethanol and deionized water, but is not limited thereto. Preferably, in order to ensure that carboxylate ions and ammonium ions in the complex molecules bound on the surfaces of the quantum dots are sufficiently separated, the quantum dot solution bound with the complex molecules is stirred and heated for 30-120 min.
The following is a further explanation of a quantum dot ligand exchange method of the present invention by means of specific examples:
example 1
1) And preparing a complexing molecule: stirring 10mmol of thioglycollic acid and 10mmol of octylamine at 40 ℃ for a period of time to fully react to obtain a complex molecule, wherein the complex molecule is a complex molecule containing a sulfhydryl functional group.
2) Ligand exchange of quantum dots: dispersing 100mg of CdSe/ZnS quantum dots into 10ml of toluene reagent, then adding all the complexing molecules in the step 1) into the quantum dot solution, and stirring at 100 ℃ to ensure that the CdSe/ZnS quantum dots and the complexing molecules fully perform ligand exchange reaction.
3) And preparing the water-phase quantum dots: adding 5ml of deionized water into the quantum dot solution exchanged in the step 2), heating and stirring the quantum dot mixed solution at 60 ℃ for 60min to completely disperse the quantum dots in the water, and stopping stirring to prepare the water-soluble quantum dot solution.
In summary, the invention provides a quantum dot ligand exchange method, in which a complex molecule generated by mixing mercaptocarboxylic acid and organic amine is mixed with a quantum dot, so that the complex molecule and a ligand on the surface of the quantum dot perform an exchange reaction to obtain a quantum dot solution with the surface bound with the complex molecule; and mixing the quantum dot solution with the surface combined with the complexing molecules with a polar solvent and carrying out heat treatment to obtain the quantum dot with the surface combined with the mercapto carboxylic acid. The invention can realize the complete exchange of the ligands on the surface of the quantum dot, thereby reducing the defects on the surface of the quantum dot.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method of quantum dot ligand exchange, comprising the steps of:
mixing mercaptocarboxylic acid and organic amine to generate a complex molecule, wherein the complex molecule is formed by combining carboxylate ions in the mercaptocarboxylic acid and ammonium ions in the organic amine;
mixing the complexing molecules with quantum dots to perform an exchange reaction between the complexing molecules and ligands on the surfaces of the quantum dots to obtain the quantum dots with the complexing molecules bound on the surfaces;
and mixing the quantum dots with the surface combined with the complexing molecules with a polar solvent to obtain the quantum dots with the surface combined with the mercapto carboxylic acid.
2. The quantum dot ligand exchange method of claim 1, wherein the chemical structural formula of the mercaptocarboxylic acid is HS- (CH)2)n-COOH, wherein n is an integer of 1 or more and 11 or less.
3. The quantum dot ligand exchange method of claim 1, wherein the organic amine has a chemical structural formula of CH3-(CH2)m-NH2Wherein m is an integer of 7 or more and 17 or less.
4. The quantum dot ligand exchange method of claim 1, wherein the mercapto carboxylic acid and the organic amine are mixed, and the carboxylate ions in the mercapto carboxylic acid and the ammonium ions in the organic amine are combined at a temperature of 30-100 ℃ to form the complex molecule.
5. The quantum dot ligand exchange method according to claim 4, wherein the mercaptocarboxylic acid and the organic amine are mixed in a molar weight ratio of 1: 1-2.
6. The quantum dot ligand exchange method according to claim 1, wherein the molar weight of the complexing molecule to the mass ratio of the quantum dot is 1-10 mmol: 100mg, mixing the complexing molecule with the quantum dots.
7. The quantum dot ligand exchange method according to claim 1, wherein the complexing molecule is mixed with the quantum dot at a temperature of 60-200 ℃ to perform an exchange reaction between the complexing molecule and the ligand on the surface of the quantum dot, thereby obtaining the quantum dot with the complexing molecule bound to the surface.
8. The quantum dot ligand exchange method according to claim 1, wherein the quantum dot with the surface bound with the complexing molecule is mixed with a polar solvent at a temperature of 30-100 ℃ to obtain the quantum dot with the surface bound with the mercaptocarboxylic acid.
9. The quantum dot ligand exchange method of claim 1, wherein the polar solvent is selected from one or more of methanol, ethanol, and deionized water.
10. The quantum dot ligand exchange method of claim 1, wherein the quantum dots are selected from one or more of binary phase quantum dots, ternary phase quantum dots, and quaternary phase quantum dots.
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| CN102159503A (en) * | 2008-07-19 | 2011-08-17 | 纳米技术有限公司 | Method for producing aqueous compatible nanoparticles |
| CN103013490A (en) * | 2012-12-07 | 2013-04-03 | 深圳康美生物科技股份有限公司 | Method for functionalizing quantum dot biomolecules |
| CN108977193A (en) * | 2017-05-31 | 2018-12-11 | Tcl集团股份有限公司 | A kind of surface is the preparation method of the quantum dot of water-soluble deprotonation ligand |
| CN108977194A (en) * | 2017-05-31 | 2018-12-11 | Tcl集团股份有限公司 | A kind of surface ligand is the preparation method of the quantum dot of deprotonation carboxylic acid |
| CN108977195A (en) * | 2017-05-31 | 2018-12-11 | Tcl集团股份有限公司 | A kind of surface ligand is the preparation method of the quantum dot of deprotonation sulfydryl |
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| CN102159503A (en) * | 2008-07-19 | 2011-08-17 | 纳米技术有限公司 | Method for producing aqueous compatible nanoparticles |
| CN107057678A (en) * | 2008-07-19 | 2017-08-18 | 纳米技术有限公司 | The method for preparing aqueous compatible nanoparticles |
| CN103013490A (en) * | 2012-12-07 | 2013-04-03 | 深圳康美生物科技股份有限公司 | Method for functionalizing quantum dot biomolecules |
| CN108977193A (en) * | 2017-05-31 | 2018-12-11 | Tcl集团股份有限公司 | A kind of surface is the preparation method of the quantum dot of water-soluble deprotonation ligand |
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| CN108977195A (en) * | 2017-05-31 | 2018-12-11 | Tcl集团股份有限公司 | A kind of surface ligand is the preparation method of the quantum dot of deprotonation sulfydryl |
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