CN108977192A - A kind of surface ligand is the preparation method of the quantum dot of deprotonation amine - Google Patents

A kind of surface ligand is the preparation method of the quantum dot of deprotonation amine Download PDF

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CN108977192A
CN108977192A CN201710400293.6A CN201710400293A CN108977192A CN 108977192 A CN108977192 A CN 108977192A CN 201710400293 A CN201710400293 A CN 201710400293A CN 108977192 A CN108977192 A CN 108977192A
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amine
quantum dot
chloride
deprotonation
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覃辉军
杨行
杨一行
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TCL Corp
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TCL Corp
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Priority to PCT/CN2018/079531 priority patent/WO2018219019A1/en
Priority to US16/617,966 priority patent/US11214732B2/en
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Abstract

The present invention discloses a kind of preparation method for the quantum dot that surface ligand is deprotonation amine, wherein comprising steps of pre-processing using acyl chlorides or sulfonic acid chloride to amine containing proton, obtains corresponding deprotonation amine aqueous solution;Pre-configured first wife's body quantum dot solution is mixed with the deprotonation amine aqueous solution, after stirring the predetermined time at room temperature, ligand exchange reaction occurs, the quantum dot that surface ligand is deprotonation amine is obtained after cleaning;Surface ligand provided by the invention is that the preparation method reaction rate of the quantum dot of deprotonation amine is fast, the cation of deprotonation amine and quantum dot surface after exchange is firmly combined, and the surface ligand finally obtained is that deprotonation amine quantum dot colloidal solution stability is strong, luminous efficiency is high.

Description

A kind of surface ligand is the preparation method of the quantum dot of deprotonation amine
Technical field
The present invention relates to a kind of preparations for the quantum dot that technology of quantum dots field more particularly to surface ligand are deprotonation amine Method.
Background technique
Fluorescence semiconductor is nanocrystalline, also known as quantum dot, and compared with conventional fluorescent dye molecule, quantum dot has many uniquenesses Luminescent properties, such as: resistance to photobleaching, excitation wave band, the features such as transmitting band gap is adjustable, therefore be widely used in photoelectric device with And the fields such as biomedicine.
Preparing the most common method of quantum dot at present is that anion predecessor is injected gold at high temperature using heat injection hair Reaction generates quantum dot in category-organic cation predecessor, and the organic matter introduced in zwitterion predecessor includes chemical combination containing P Object, chain alkyl acid, amine etc., the introducing of these organic matters is adjustable the crystal growth rate, crystal morphology, crystalline substance of quantum dot The distribution of body size.In addition, these organic matters can reduce surface defect as the surface end-capping reagent of quantum dot to improve quantum dot hair Light efficiency.Particularly, the factors such as the functional group of surface ligand, chain length determine the electronic structure of itself, so as to influence amount The surface electronic hole wave functions of son point and the electronic transmission performance of quantum dot film layer.Wherein amino ligands and CdSe quantum When point surface combines, the shell structurre of quantum dot can be directly served as to improve the luminous efficiency of quantum dot, do not need regrowth Inorganic shell structurre.In addition, amino ligand can also be combined with the cation for not participating in reaction, purified for quantum dot.However, In quantum dot ligand exchange processes, amino ligands are directly added into quantum dot reaction solution and stir, the quantum being prepared Amino ligands and quantum dot surface binding ability are weak in point, and quantum dot colloidal solution ligand is easy to fall off after a long time placement, particle Reunite and generate precipitating, therefore how to make amino ligands effectively in conjunction with quantum dot, however it remains biggish challenge.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide the amounts that a kind of surface ligand is deprotonation amine The preparation method of son point, it is intended to which it is insecure with ligand binding to solve existing quantum dot surface, causes quantum dot colloidal solution steady The problem of qualitative difference.
Technical scheme is as follows:
A kind of surface ligand is the preparation method of the quantum dot of deprotonation amine, wherein comprising steps of
A, amine containing proton is pre-processed using acyl chlorides or sulfonic acid chloride, obtains corresponding deprotonation amine aqueous solution;
B, pre-configured first wife's body quantum dot solution is mixed with the deprotonation amine aqueous solution, stirs the predetermined time at room temperature Afterwards, ligand exchange reaction occurs, the quantum dot that surface ligand is deprotonation amine is obtained after cleaning.
The surface ligand be deprotonation amine quantum dot preparation method, wherein in step, the acyl chlorides or The molar ratio of sulfonic acid chloride and the amine containing proton is 1:1-6.
The surface ligand be deprotonation amine quantum dot preparation method, wherein the amine containing proton be alkylamine, One of mercapto-amine, amino acid or amide.
The surface ligand is the preparation method of the quantum dot of deprotonation amine, wherein the alkylamine is methylamine, diformazan Amine, ethamine, Methylethyl amine, ethylenediamine, propylamine, butylamine, three-level butylamine, amylamine, n-hexylamine, cyclohexylamine, methylhexyl amine, heptan Amine, two heptyl amices, octylame, two n-octyl amines, nonyl amine, 4- octyl aniline, N, N '-dimethyl -1,8- octamethylenediamine, bis- (2- ethylhexyls) In amine, aniline, benzene methanamine, open-chain crown ether, N- toluidines, lauryl amine, tetradecy lamine, cetylamine, octadecylamine or octadecenyl amine It is a kind of.
The surface ligand is the preparation method of the quantum dot of deprotonation amine, wherein the mercapto-amine is 2- sulfydryl second Amine, 3- mercaptopropylamine, 4- sulfydryl butylamine, 5- sulfydryl amylamine, 6- sulfydryl hexylamine, 2- amino-3-mercaptopropionic acid, 2- aminothiophenol Or one of mercaptoundecylamine.
The surface ligand is the preparation method of the quantum dot of deprotonation amine, wherein the amino acid is glycine, third One in propylhomoserin, valine, leucine, isoleucine, cysteine, phenylalanine, glutamic acid, asparagine or lysine Kind;The amide is formamide, acetamide, propionamide, butyramide, pentanamide, caproamide, asparagine, picolinamide, bigcatkin willow One of amide or 2-TETRAHYDROFUROYL amine.
The surface ligand is the preparation method of the quantum dot of deprotonation amine, wherein the acyl chlorides is chloroacetic chloride, propionyl Chlorine, butyl chloride, valeric chloride, caproyl chloride, 2- chlorpromazine chloride, 3- chlorpromazine chloride, 4- chlorobutanoylchloride, 1- butyl sulfochlorides, 1- 16 Alkanesulphonyl chlorides, 1- perfluorooctane sulfonyl chlorine, 1,7- pimeloyl chloride, three formyl chloride of 1,3,5- benzene, 4- chlorobenzoyl chloride, 5- chlorine valeryl One of chlorine, 6- chlorine caproyl chloride or 2- chloropyridine -4- formyl chloride.
The surface ligand is the preparation method of the quantum dot of deprotonation amine, wherein the sulfonic acid chloride is sulfonyloxy methyl Chlorine, ethyl chloride, sulfonyl propyl chlorine, butyl sulfochlorides, amyl sulfonic acid chloride, hexyl sulfonic acid chloride, perfluorooctane sulfonyl chlorine, hexadecane sulphur Acyl chlorides, 2- chloroethene alkanesulphonyl chlorides, benzene sulfonyl chloride or to one of benzene sulfonyl chloride.
The surface ligand is the preparation method of the quantum dot of deprotonation amine, wherein in the step B further include:
After the completion of ligand exchange reaction, 10-30min is stood, after being eventually adding ethyl acetate centrifugation 2-4 times, surface is obtained and matches Body is the quantum dot of deprotonation amine.
The surface ligand is the preparation method of the quantum dot of deprotonation amine, wherein in stepb, first wife's body The molar ratio of quantum dot and the deprotonation amine aqueous solution is 1:1-8.
The utility model has the advantages that the present invention provides a kind of preparation method for the quantum dot that surface ligand is deprotonation amine, wherein first will Amine containing proton is pre-processed with acyl chlorides or sulfonic acid chloride, obtains deprotonation amine aqueous solution;Then by the deprotonation amine aqueous solution and original Ligand quantum dot solution is mixed, and carries out ligand exchange reaction, and the quantum dot that surface is deprotonation amine is obtained after cleaning;This hair The surface ligand of bright offer is that the preparation method reaction rate of the quantum dot of deprotonation amine is fast, deprotonation amine and quantum after exchange The cation on point surface is firmly combined, and the surface ligand finally obtained is that deprotonation amine quantum dot colloidal solution stability is strong, sends out Light efficiency is high.
Detailed description of the invention
Fig. 1 is the process of the preparation method preferred embodiment for the quantum dot that a kind of surface ligand of the present invention is deprotonation amine Figure.
Fig. 2 is the launching light spectrogram in the embodiment of the present invention 1 before and after quantum dot ligand exchange.
Fig. 3 is the map that the relative luminous intensity in the embodiment of the present invention 1 before and after quantum dot ligand exchange changes over time.
Fig. 4 is not have in the embodiment of the present invention 2/pre-processed ligand to solution after quantum dot ligand exchange with proton-removed agent Absorption curve schematic diagram.
Specific embodiment
The present invention provides a kind of preparation method for the quantum dot that surface ligand is deprotonation amine, for make the purpose of the present invention, Technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that described herein Specific embodiment is only used to explain the present invention, is not intended to limit the present invention.
Referring to Fig. 1, the preparation method that Fig. 1 is the quantum dot that a kind of surface ligand of the present invention is deprotonation amine is preferably implemented The flow chart of example, as shown in the figure, wherein comprising steps of
S10, amine containing proton is pre-processed using acyl chlorides or sulfonic acid chloride, obtains corresponding deprotonation amine aqueous solution;
S20, pre-configured first wife's body quantum dot solution is mixed with the deprotonation amine aqueous solution, at room temperature the pre- timing of stirring Between after, occur ligand exchange reaction, obtained after cleaning surface ligand be deprotonation amine quantum dot.
Specifically, when surface ligand of the proton amine directly as quantum dot will be contained, amino in the amine containing proton (- NH2) H be in free state, at this time functional group (- NH2) with quantum dot with coordinate bond in conjunction with correspondingly generate-NH (H)-R, wherein R is Quantum dot surface cation;And-NH- is easy to the H of free state in conjunction with to be detached from life with quantum dot surface cation At amine;This quantum dot colloidal solution stability for directly generating amine containing proton in conjunction with quantum dot is very poor, ligand and quantum Point combination is extremely insecure;
Insecure in conjunction with amine containing proton, the problem of the quantum dot colloidal solution stability difference of generation, this hair for solution quantum dot The bright preparatory H for using acyl chlorides or sulfonic acid chloride (i.e. proton-removed agent) to handle the amine containing proton, removing in amine containing proton, obtains To corresponding deprotonation amine aqueous solution;
Further, the step S10 specifically: the acyl chlorides is added in amine aqueous solution containing proton or sulfonic acid chloride is reacted, institute The molar ratio for stating acyl chlorides or sulfonic acid chloride and the amino ligands containing proton is 1:1-6, preferably 1:3;Further, molten to the amine containing proton After liquid is mixed with the acyl chlorides or sulfonic acid chloride, reaction 5-120min is stirred at room temperature, after being then allowed to stand 10-30min, has reacted Corresponding deprotonation amine ligand solution is made after complete.
Specifically, the proton-removed agent is one of acyl chlorides or sulfonic acid chloride, when the proton-removed agent is acyl chlorides, with The reaction of amine containing proton generates amide R1CONHR2(R, R2For alkyl);When the proton-removed agent is sulfonamide, with amine containing proton Reaction generates sulfonamide R1SO2NHR2(R, R2For alkyl);
It is described when being mixed by the deprotonation amine ligand (amide or sulfonamide) that proton-removed agent is handled with first wife's body quantum dot solution Deprotonation amine ligand and quantum dot surface cation are with X-NHR2(X is quantum dot surface cation, R2For alkyl) it combines, at this time H and ligand binding without free state, therefore, the quantum dot and deprotonation amine ligand are not easily to fall off, and stability is stronger.
Further, in the present invention, the amine containing proton is one of alkylamine, mercapto-amine, amino acid or amide, tool Body, the alkylamine be methylamine, dimethylamine, ethamine, Methylethyl amine, ethylenediamine, propylamine, butylamine, three-level butylamine, amylamine, N-hexylamine, cyclohexylamine, methylhexyl amine, heptyl amice, two heptyl amices, octylame, two n-octyl amines, nonyl amine, 4- octyl aniline, N, N '-diformazan Base -1,8- octamethylenediamine, bis- (2- ethylhexyl) amine, aniline, benzene methanamine, open-chain crown ether, N- toluidines, lauryl amine, tetradecy lamine, Any one in cetylamine, octadecylamine or octadecenyl amine, but not limited to this;
The mercapto-amine is 2-MEA, 3- mercaptopropylamine, 4- sulfydryl butylamine, 5- sulfydryl amylamine, 6- sulfydryl hexylamine, 2- ammonia Any one in base -3- mercaptopropionic acid, 2- aminothiophenol or mercaptoundecylamine, but not limited to this;
The amino acid is glycine, alanine, valine, leucine, isoleucine, cysteine, phenylalanine, paddy ammonia Any one in acid, asparagine or lysine, but not limited to this;
The amide is formamide, acetamide, propionamide, butyramide, pentanamide, caproamide, asparagine, picolinamide, water Any one in poplar amide or 2-TETRAHYDROFUROYL amine, but not limited to this.
Further, when the amine ligand containing proton is oil-soluble ligand, such as when thiol ligand is octadecylamine, at this time After proton-removed agent and the octadecylamine fully reacting, solution generates split-phase, at this time should remove water phase, obtains containing by liquid separation and go The oil-phase solution of proton octadecylamine.The presence of water phase will affect oil-soluble deprotonation ligand and first wife's body quantum dot occurs ligand and hands over Reaction is changed, causes to exchange the quantum dot light emitting efficiency reduction after ligand.
Further, in the present invention, the proton-removed agent is one of acyl chlorides or sulfonic acid chloride;Specifically, the acyl chlorides For chloroacetic chloride, propionyl chloride, butyl chloride, valeric chloride, caproyl chloride, 2- chlorpromazine chloride, 3- chlorpromazine chloride, 4- chlorobutanoylchloride, 1- butyl Sulfonic acid chloride, 1- hexadecane sulfonic acid chloride, 1- perfluorooctane sulfonyl chlorine, 1,7- pimeloyl chloride, three formyl chloride of 1,3,5- benzene, 4- chlorobenzene Any one in formyl chloride, 5-Chlorovaleryl Chloride, 6- chlorine caproyl chloride or 2- chloropyridine -4- formyl chloride, but not limited to this;
The sulfonic acid chloride is methylsufonyl chloride, ethyl chloride, sulfonyl propyl chlorine, butyl sulfochlorides, amyl sulfonic acid chloride, hexyl sulphur Acyl chlorides, perfluorooctane sulfonyl chlorine, hexadecane sulfonic acid chloride, 2- chloroethene alkanesulphonyl chlorides, benzene sulfonyl chloride or to any one in benzene sulfonyl chloride, But not limited to this.
Further, in the step S20, by pre-configured first wife's body quantum dot solution and the amide or sulphonyl After stirring the predetermined time at room temperature, ligand exchange reaction occurs for amine aqueous solution mixing, and the quantum that surface ligand is deprotonation amine is made Point colloidal solution.
In particular it is necessary to be pre-configured with first wife's body quantum dot solution, first wife's body is tri octyl phosphine, trioctylphosphine oxidation One of phosphine, tributylphosphine, tributylphosphine oxide, oleic acid or stearic acid;These first wife's bodies are blocked as the surface of quantum dot Agent can reduce quantum dot surface defect to improve the luminous efficiency of quantum dot, however these first wife's bodies and quantum dot have knot Conjunction ability is weak, formation quantum dot colloidal solution stability is poor and the various problems such as dissolubility is poor;
Specifically, the present invention mixes pre-configured first wife's body quantum dot solution with the deprotonation amine aqueous solution, the original The molar ratio of ligand quantum dot and deprotonation amine aqueous solution is 1:1-8, preferably 1:3;It is lasting to stir during ligand exchange reaction 5-120min;Specifically, ligand exchange occurs after first wife's body quantum dot solution is mixed with the deprotonation amine aqueous solution Reaction, lasting stirring can accelerate to react and make reaction more evenly.After the completion of ligand exchange reaction, 10-30min is stood, most After ethyl acetate centrifugation 2-4 times is added afterwards, the quantum dot that surface ligand is deprotonation amine is obtained.
Further, the quantum dot is CdSe, CdS, ZnSe, ZnS, PbSe, PbS, CdTe, Cd1-xZnxS、Cd1- xZnxSe、CdSeyS1-y、Cd1-xZnxSeyS1-y、PbSeXS1-X、ZnXCd1-XTe、CdSe/ ZnS、CdS/ ZnS、Cd1-xZnxSe/ ZnS、Cd1-xZnxS/ ZnS、CdSe/CdS/ZnS、CdSe/ZnSe/ZnS、CdS/Cd1-xZnxS/CdyZn1-yS/ZnS、CdSe/ Cd1-xZnxSe/CdyZn1-ySe /ZnSe、InP、InP/ZnS、ZnO、MgO、CeO2、NiO、TiO2、CaF2、NaYF4Or NaCdF4 Any one in, but not limited to this luminescent quantum dot.
Surface ligand provided by the invention is that the preparation method reaction rate of the quantum dot of deprotonation amine is fast, is gone after exchange The cation of proton amine and quantum dot surface is firmly combined, and the quantum dot colloidal solution stability finally obtained is strong and the effect that shines Rate is high.
It is done below by preparation method of the specific embodiment to the quantum dot that a kind of surface ligand of the present invention is deprotonation amine It further explains:
Embodiment 1
1, surface ligand is the preparation of the quantum dot of octadecenic acid:
1) 0.8mmolCdO, 8mmol zinc acetate and 15 ml oleic acid and 20 ml1- ten, cadmium oleate-zinc precursor liquid preparation: are taken Eight alkene are heated to 150 DEG C of exhaust 1h under an ar atmosphere, it is molten to form transparent cadmium oleate-zinc precursor in 100mL three-necked flask Liquid;
2), the preparation of Se-S-ODE precursor liquid: 0.8 mmol Se and 8 mmol S is taken to be dissolved in 6 mL1- octadecylenes at 140 DEG C molten In liquid, Se-S-ODE precursor liquid is formed;
3) cadmium oleate-zinc precursor liquid, is heated slowly to 300 DEG C, is once rapidly injected Se-S-ODE precursor liquid, reaction maintains 8 min.Then temperature is reduced to 100 DEG C, ethyl acetate cleaning is added, centrifugation obtains sediment;Then chloroform and acetone is added It is centrifuged repeatedly 2 times, obtains the quantum dot that surface ligand is octadecenic acid and precipitate.
2, the deprotonation of ligand containing proton:
It takes 4 mmol propionyl chlorides, 4 mmol octylames to be added in chloroformic solution, 30min is stirred at room temperature, obtain propionyl chloride processing The octylame solution crossed.
3, ligand exchange processes:
The quantum dot that surface ligand is octadecenic acid is made into the chloroformic solution of 10mg/ml, above-mentioned propionyl chloride processing is then added 60 min are stirred at room temperature in the octylame solution crossed, and stand 15 min, and ethyl acetate is added and is centrifuged 2 times, obtaining surface ligand is The quantum dot of deprotonation octylame.
Further, Fig. 2 is the launching light spectrogram in embodiment 1 before and after quantum dot ligand exchange, as shown in Figure 2, quantum dot Its luminous intensity increases after ligand exchange;It, can effectively and quantum dot surface after explanation is handled ligand with proton-removed agent Cation combines, and surface defect is reduced, to improve luminous efficiency.
Further, Fig. 3 is the figure that the relative luminous intensity in embodiment 1 before and after quantum dot ligand exchange changes over time Spectrum, from the figure 3, it may be seen that it is low that the luminous intensity of quantum dot changes over time decline degree after ligand exchange;This same explanation spends matter , can be not easily to fall off effectively in conjunction with quantum dot surface cation after sub- agent handles ligand, surface defect is reduced, thus Improve luminous efficiency.
Embodiment 2
1, surface ligand is the preparation of stearic ZnO quantum dot:
1), the preparation of zinc stearate precursor liquid: take 2mmol zinc stearate that 30 ml ODE Ar exhaust 30 at 130 DEG C is added Min, solution become colorless and transparent, obtain zinc stearate precursor liquid;
2), the preparation of long-chain alcohol precursor liquid: taking 10 mmol ODA to be dissolved in 12.6 ml ODE, 30 min be vented at 130 DEG C, Solution is colorless and transparent, then is warming up to 200 DEG C for molten, obtains long-chain alcohol precursor liquid;
3), the preparation of ZnO quantum dot: being warming up to 270 DEG C for zinc stearate solution, then once quickly infuses long-chain alcoholic solution Enter in zinc stearate solution, reaction maintains 250 DEG C of 4 min of holding.Then solution is cooled to room temperature, cleans 2 times, is sunk Starch is dried in vacuo 24 h at room temperature, obtains dry ZnO crystal;
2, the deprotonation of ligand containing proton:
It takes 4 mmol benzene sulfonyl chlorides, 8 mmol phenylalanines to be added in aqueous solution, 30min is stirred at room temperature, obtains benzene sulfonyl The processed Phe solution of chlorine.
3, ligand exchange processes:
Taking 100mg surface ligand is that stearic quantum dot is added in 10ml n-hexane, is uniformly mixed, above-mentioned benzene sulphur is then added 60 min are stirred at room temperature in the processed Phe solution of acyl chlorides, stand 15 min, and ethyl acetate is added and is centrifuged 2 times, obtains It is the quantum dot of deprotonation phenylalanine to surface ligand.
Further, Fig. 4 be without/with proton-removed agent ligand is pre-processed it is bent to the absorption of solution after quantum dot ligand exchange Line;As shown in figure 4, the quantum dot dissolubility obtained after wherein pre-processing without proton-removed agent to ligand is low, solution bottom There are a large amount of precipitatings, the quantum dot dissolubility obtained after being pre-processed with proton-removed agent to ligand is high.Take the stillness of night of two parts of solution Uv-visible absorption spectra test is carried out, if not carrying out deprotonation processing to ligand as seen from the figure, quantum dot solution absorbs bent There is no the band edge of ZnO to absorb in line.And after carrying out deprotonation processing to ligand, solution has the band edge absorption peak of ZnO.Explanation is gone After proton ligand pre-processes ligand, the dissolubility of quantum dot can effectively improve.
Embodiment 3
1, surface ligand is the preparation of the quantum dot of octadecenic acid:
1) 0.8mmolCdO, 8mmol zinc acetate and 15 ml oleic acid and 20 ml1- ten, cadmium oleate-zinc precursor liquid preparation: are taken Eight alkene are heated to 150 DEG C of exhaust 1h under an ar atmosphere, it is molten to form transparent cadmium oleate-zinc precursor in 100mL three-necked flask Liquid;
2), the preparation of Se-S-ODE precursor liquid: 0.8 mmol Se and 8 mmol S is taken to be dissolved in 6 mL1- octadecylenes at 140 DEG C molten In liquid, Se-S-ODE precursor liquid is formed;
3) cadmium oleate-zinc precursor liquid, is heated slowly to 300 DEG C, is once rapidly injected Se-S-ODE precursor liquid, reaction maintains 8 min.Then temperature is reduced to 100 DEG C, ethyl acetate cleaning is added, centrifugation obtains sediment;Then chloroform and acetone is added It is centrifuged repeatedly 2 times, obtains the quantum dot that surface ligand is octadecenic acid and precipitate.
2, the deprotonation of ligand containing proton:
It takes 4 mmol benzene sulfonyl chlorides, 4 mmol aniline to be added in aqueous solution, 30min is stirred at room temperature, obtains at benzene sulfonyl chloride The aniline solution managed.
3, ligand exchange processes:
The quantum dot that surface ligand is octadecenic acid is made into the chloroformic solution of 10mg/ml, is then added at above-mentioned benzene sulfonyl chloride 60 min are stirred at room temperature in the aniline solution managed, and stand 15 min, and ethyl acetate is added and is centrifuged 2 times, obtains surface ligand For the quantum dot of deprotonation aniline.
In conclusion the present invention provides a kind of preparation method for the quantum dot that surface ligand is deprotonation amine, wherein first will Amine containing proton is pre-processed with acyl chlorides or sulfonic acid chloride, obtains deprotonation amine aqueous solution;Then by the deprotonation amine aqueous solution and original Ligand quantum dot solution is mixed, and carries out ligand exchange reaction, and the quantum dot that surface is deprotonation amine is obtained after cleaning;This hair The surface ligand of bright offer is that the preparation method reaction rate of the quantum dot of deprotonation amine is fast, deprotonation amine and quantum after exchange The cation on point surface is firmly combined, and the surface ligand finally obtained is that deprotonation amine quantum dot colloidal solution stability is strong, sends out Light efficiency is high.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention Protect range.

Claims (10)

1. the preparation method that a kind of surface ligand is the quantum dot of deprotonation amine, which is characterized in that comprising steps of
A, amine containing proton is pre-processed using acyl chlorides or sulfonic acid chloride, obtains corresponding deprotonation amine aqueous solution;
B, pre-configured first wife's body quantum dot solution is mixed with the deprotonation amine aqueous solution, stirs the predetermined time at room temperature Afterwards, ligand exchange reaction occurs, the quantum dot colloidal solution that surface ligand is deprotonation amine is made.
2. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation amine, which is characterized in that in step In rapid A, the molar ratio of the acyl chlorides or sulfonic acid chloride and the amine containing proton is 1:1-6.
3. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation amine, which is characterized in that described Amine containing proton is one of alkylamine, mercapto-amine, amino acid or amide.
4. the preparation method that surface ligand according to claim 3 is the quantum dot of deprotonation amine, which is characterized in that described Alkylamine is methylamine, dimethylamine, ethamine, Methylethyl amine, ethylenediamine, propylamine, butylamine, three-level butylamine, amylamine, n-hexylamine, ring Hexylamine, methylhexyl amine, heptyl amice, two heptyl amices, octylame, two n-octyl amines, nonyl amine, 4- octyl aniline, N, N '-dimethyl -1,8- are pungent Diamines, bis- (2- ethylhexyl) amine, aniline, benzene methanamine, open-chain crown ether, N- toluidines, lauryl amine, tetradecy lamine, cetylamine, ten One of eight amine or octadecenyl amine.
5. the preparation method that surface ligand according to claim 3 is the quantum dot of deprotonation amine, which is characterized in that described Mercapto-amine is 2-MEA, 3- mercaptopropylamine, 4- sulfydryl butylamine, 5- sulfydryl amylamine, 6- sulfydryl hexylamine, 2- amino -3- sulfydryl One of propionic acid, 2- aminothiophenol or mercaptoundecylamine.
6. the preparation method that surface ligand according to claim 3 is the quantum dot of deprotonation amine, which is characterized in that described Amino acid is glycine, alanine, valine, leucine, isoleucine, cysteine, phenylalanine, glutamic acid, asparagus fern acyl One of amine or lysine;The amide is formamide, acetamide, propionamide, butyramide, pentanamide, caproamide, asparagus fern acyl One of amine, picolinamide, salicylamide or 2-TETRAHYDROFUROYL amine.
7. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation amine, which is characterized in that described Acyl chlorides is chloroacetic chloride, propionyl chloride, butyl chloride, valeric chloride, caproyl chloride, 2- chlorpromazine chloride, 3- chlorpromazine chloride, 4- chlorobutanoylchloride, 1- Butyl sulfochlorides, 1- hexadecane sulfonic acid chloride, 1- perfluorooctane sulfonyl chlorine, 1,7- pimeloyl chloride, three formyl chloride of 1,3,5- benzene, 4- chlorobenzene first One of acyl chlorides, 5-Chlorovaleryl Chloride, 6- chlorine caproyl chloride or 2- chloropyridine -4- formyl chloride.
8. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation amine, which is characterized in that described Sulfonic acid chloride is methylsufonyl chloride, ethyl chloride, sulfonyl propyl chlorine, butyl sulfochlorides, amyl sulfonic acid chloride, hexyl sulfonic acid chloride, pungent Alkanesulphonyl chlorides, hexadecane sulfonic acid chloride, 2- chloroethene alkanesulphonyl chlorides, benzene sulfonyl chloride or to one of benzene sulfonyl chloride.
9. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation amine, which is characterized in that described In step B further include:
After the completion of ligand exchange reaction, 10-30min is stood, after being eventually adding ethyl acetate centrifugation 2-4 times, surface is obtained and matches Body is the quantum dot of deprotonation amine.
10. the preparation method that surface ligand according to claim 1 is the quantum dot of deprotonation amine, which is characterized in that In step B, the molar ratio of first wife's body quantum dot and deprotonation amine aqueous solution is 1:1-8.
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CN113912587A (en) * 2020-07-10 2022-01-11 Tcl科技集团股份有限公司 Surface ligand, quantum dot and preparation method thereof, and quantum dot light-emitting diode

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN108997999A (en) * 2018-06-14 2018-12-14 苏州星烁纳米科技有限公司 Quantum dot and preparation method thereof
CN110330517A (en) * 2019-05-22 2019-10-15 纳晶科技股份有限公司 Alcohol-soluble quantum dot and preparation method thereof, quantum dot film, quantum dot optoelectronic devices
CN110330517B (en) * 2019-05-22 2022-04-19 纳晶科技股份有限公司 Alcohol-soluble quantum dot, preparation method thereof, quantum dot film and quantum dot photoelectric device
CN113912587A (en) * 2020-07-10 2022-01-11 Tcl科技集团股份有限公司 Surface ligand, quantum dot and preparation method thereof, and quantum dot light-emitting diode
CN113912587B (en) * 2020-07-10 2023-01-31 Tcl科技集团股份有限公司 Surface ligand, quantum dot and preparation method thereof, and quantum dot light-emitting diode

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