CN111849459A - Waterproof oxygen quantum dot and preparation method thereof - Google Patents
Waterproof oxygen quantum dot and preparation method thereof Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 121
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- 239000001301 oxygen Substances 0.000 title claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 13
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- 239000000243 solution Substances 0.000 claims description 52
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 36
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- 238000000034 method Methods 0.000 claims description 14
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 8
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 8
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 7
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229940057995 liquid paraffin Drugs 0.000 claims description 4
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
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- 239000005871 repellent Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002608 ionic liquid Substances 0.000 description 7
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
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- 238000006862 quantum yield reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- ZPGIVLOUVWCNHK-UHFFFAOYSA-N C(CC)[Zr] Chemical compound C(CC)[Zr] ZPGIVLOUVWCNHK-UHFFFAOYSA-N 0.000 description 1
- FGQRHNWAVSBJHZ-UHFFFAOYSA-N CCCC[Zr] Chemical compound CCCC[Zr] FGQRHNWAVSBJHZ-UHFFFAOYSA-N 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 238000002189 fluorescence spectrum Methods 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/621—Chalcogenides
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- 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 provides a waterproof oxygen quantum dot and a preparation method thereof. The preparation method comprises the following steps: mixing the quantum dot solution with the metal precursor solution, and heating and reacting under the atmosphere of protective gas to obtain a reacted solution; and cooling the reacted liquid, carrying out solid-liquid separation and purification to obtain the waterproof oxygen quantum dots. The quantum dot has the advantages of strong oxygen waterproof capability, high stability, simple preparation method and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of quantum dots, relates to a method for improving the stability of quantum dots, and particularly relates to a waterproof oxygen quantum dot and a preparation method thereof.
Background
The quantum dot is a nano semiconductor material, has excellent optical performance, and can obtain quantum dot materials with different emission wavelengths from ultraviolet to visible light to infrared and the like through size or component adjustment. The quantum dot has the advantages of simple synthesis process, wide raw materials, tunable wavelength, close to 100% of fluorescence quantum yield, narrow emission peak and high color purity of light, and has great potential and commercial value in the display field.
As a light conversion material, the quantum dots can convert blue backlight into light with other different colors, and in the process, moisture and oxygen in the air can slowly erode the quantum dots, so that ligands on the surfaces of the quantum dots fall off or surface elements are oxidized, the defects of the quantum dots are increased, the optical performance of the quantum dots is reduced, and the use of the quantum dots is influenced.
In order to overcome the influence of water and oxygen on the quantum dots and improve the stability of the quantum dots, the simplest and most direct method is to isolate the quantum dots from water and oxygen and encapsulate the quantum dots. At present, the main encapsulation means of quantum dots are as follows: 1) encapsulating the quantum dots in glue; 2) directly embedding and dispersing the quantum dots into a polymer; 3) coating the quantum dots, such as silica and the like; 4) and (3) combining the above schemes. The method has obvious effect on improving the stability of the quantum dots, but under the long-term use condition of the quantum dots, the optical performance of the quantum dots is attenuated due to the permeability of water and oxygen of the materials or a small amount of water and oxygen entering the surfaces of the quantum dots.
CN 109679645A discloses a high-stability high-quantum-efficiency perovskite quantum dot synthesis method, which enables perovskite quantum dots to react between montmorillonite layers through the adsorption effect between montmorillonite and cations, and perovskite nano particles are separated by a lamellar structure, so that the free ion exchange between the perovskite quantum dots can be effectively reduced, and meanwhile, the lamellar structure has high water vapor and oxygen blocking effect, and the stability of the quantum dots is greatly improved. The method comprises the following specific steps: a. CsX is mixed with water and ethanol, and stirred fully until the mixture is dissolved completely; b. adding the sheet montmorillonite into the solution in the step a, and adsorbing Cs + cations among the montmorillonite layers; after the reaction is finished, centrifugally washing for 3 times, and dispersing in octadecene after vacuum drying; c. mixing and stirring a lead source, organic long-chain acid, organic long-chain amine and a solvent to form transparent liquid; d. rapidly injecting the dispersion liquid in the step b into the transparent liquid in the step c.
CN 107353889A discloses a method for improving stability of water phase quantum dots, ligand exchange is carried out between ionic liquid and water phase quantum dots, the boiling point of the modified quantum dot ionic liquid is very high and generally exceeds 200 ℃, the stability is higher than that of small molecular ligands used for preparing conventional water phase quantum dots, such as thioglycolic acid, mercaptopropionic acid, glutathione and the like, ligand exchange is carried out between the ionic liquid and the water phase quantum dots, the ionic liquid is used as quantum dots wrapped by the ligand, and the stability of single quantum dots is improved; the ionic liquid is an ionic crystal, the inorganic salt crystal is also an ionic crystal, the quantum dots modified by the ionic liquid can be better matched with the growth process of the inorganic salt crystal, after the ionic liquid and the inorganic salt are mixed, the agglomeration among the quantum dots is not easy to occur, the solid-state quantum dots with uniformly dispersed quantum dots and high stability can be obtained, the particle size of the solid-state quantum dots can be regulated and controlled through processes such as grinding, and then the solid-state quantum dots with different light emitting characteristics can be obtained.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a waterproof oxygen quantum dot and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a waterproof oxygen quantum dot, which is characterized in that metal ions are modified outside the quantum dot.
In a preferred embodiment of the present invention, the metal ions include titanium ions and/or zirconium ions.
As a preferred embodiment of the present invention, the quantum dots include one or a combination of at least two of CdSe, CdTe, CdS, ZnSe, CdTe, CuInS, InP, CuInSe, or CdZnSSe, and the combination is typically, but not limited to, as follows: combinations of CdSe and CdTe, CdTe and CdS, CdS and ZnSe, ZnSe and CdTe, CdTe and CuInS, CuInS and InP, InP and CuInSe, CuInSe and cdznse, cdznse and CdSe, CdTe and CdS, and the like, preferably CdSe.
According to the invention, the surface of the quantum dot is modified by other metal elements to change the environment of the surface of the quantum dot, and when water oxygen reaches the surface of the quantum dot, the difficulty of surface reaction of the water oxygen and the quantum dot is improved due to the adsorption of the modified metal elements on the surface of the quantum dot, so that the stability of the quantum dot is improved.
The second purpose of the invention is to provide a preparation method of the waterproof oxygen quantum dot, which comprises the following steps:
(1) mixing the quantum dot solution with the metal precursor solution, and heating and reacting under the atmosphere of protective gas to obtain a reacted solution;
(2) and (2) cooling the reacted liquid obtained in the step (1), and carrying out solid-liquid separation and purification to obtain the waterproof oxygen quantum dots.
As a preferred embodiment of the present invention, the concentration of the quantum dot solution in step (1) is 1 to 200mg/mL, such as 2mg/mL, 5mg/mL, 10mg/mL, 15mg/mL, 20mg/mL, 25mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 80mg/mL, 100mg/mL, 120mg/mL, 150mg/mL or 180mg/mL, but is not limited to the values listed, and other values within the range of values are also applicable.
Preferably, the solvent of the quantum dot solution in the step (1) is octadecene and/or liquid paraffin.
As a preferred technical solution of the present invention, the metal precursor in step (1) includes any one or a combination of at least two of titanium isopropoxide, tetrabutyl titanate, tetraisopropyl titanate, zirconium n-propoxide, or zirconium n-butoxide, and the combination is typically but not limited to: combinations of titanium isopropoxide and tetrabutyl titanate, tetrabutyl titanate and tetraisopropyl titanate, tetraisopropyl titanate and zirconium n-propoxide, zirconium n-propoxide and zirconium n-butoxide, or zirconium n-butoxide and titanium isopropoxide, and the like.
Preferably, the metal precursor is added in the step (1) in an amount of 0.1 to 5% by volume of the quantum dot solution, such as 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5%, but not limited to the recited values, and other values in the range are not listed and are also applicable.
As a preferred embodiment of the present invention, the temperature of the heating reaction in the step (1) is 60 to 200 ℃, for example, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, etc., but it is not limited to the recited values, and the same applies to other values within the range of the values.
Preferably, the heating reaction time in step (1) is 5-300 min, such as 10min, 20min, 50min, 80min, 100min, 120min, 150min, 180min, 200min, 220min, 250min or 280min, but not limited to the recited values, and other values in the range are not listed and are also applicable.
Preferably, the heating reaction of step (1) is carried out under stirring.
Preferably, the protective gas in step (1) comprises any one or a combination of at least two of nitrogen, helium or argon.
As a preferable technical solution of the present invention, the cooling in the step (2) is cooling the cooled liquid to room temperature.
As a preferable technical scheme of the invention, the solid-liquid separation and purification in the step (2) comprises mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, and performing centrifugal separation.
As a preferred technical solution of the present invention, the preparation method of the above-mentioned waterproof oxygen quantum dot comprises the steps of:
(1) mixing a quantum dot solution with the concentration of 1-200 mg/mL with a metal precursor solution, wherein the addition amount of the metal precursor is 0.1-5% of the volume of the quantum dot solution, and heating and stirring at 60-200 ℃ for 5-300 min under the atmosphere of protective gas to react to obtain a reacted solution;
the solvent of the quantum dot solution is octadecene and/or liquid paraffin, and the metal precursor comprises any one or the combination of at least two of titanium isopropoxide, tetrabutyl titanate, tetraisopropyl titanate, zirconium n-propoxide or zirconium n-butoxide;
(2) and (2) cooling the reacted liquid in the step (1) to room temperature, mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, and performing centrifugal separation to obtain the waterproof oxygen quantum dot.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a waterproof oxygen quantum dot and a preparation method thereof, wherein the quantum dot has strong waterproof oxygen capacity and high stability;
(2) the invention provides a waterproof oxygen quantum dot and a preparation method thereof.
Drawings
FIG. 1 is a fluorescence spectrum of a titanium ion modified quantum dot and a primary quantum dot prepared in example 1 of the present application;
FIG. 2 is a graph comparing aging tests of titanium ion modified quantum dots and original quantum dots prepared in example 1 of the present application;
fig. 3 is a TEM image of the titanium ion modified quantum dot prepared in example 1 of the present application.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of a waterproof oxygen quantum dot, which comprises the following steps:
(1) mixing an octadecene solution of CdSe quantum dots with the concentration of 50mg/mL with a titanium isopropoxide solution, wherein the addition amount of the titanium isopropoxide is 1% of the volume of the quantum dot solution, and heating and stirring the mixture at 200 ℃ for reaction for 30min under an argon atmosphere to obtain a reacted solution;
(2) and (2) cooling the reacted liquid obtained in the step (1) to room temperature, mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, wherein the volume ratio of the reacted liquid to the toluene to the ethanol is 1:1:3, and performing centrifugal separation to obtain the titanium ion modified CdSe quantum dot.
It can be seen from fig. 1 that the fluorescence peak of the titanium-treated quantum dot is almost identical to that of the original quantum dot, and only the wavelength is shifted by 3 to 4 nm.
It can be seen from fig. 2 that the stability of the quantum dots after the titanium treatment is better than that of the original quantum dots
It can be seen from fig. 3 that the reason why the stability of the quantum dot after the titanium treatment is better than that of the original quantum dot is that the thick coating of titanium is not formed on the surface of the quantum dot, but is modified on the surface of the quantum dot.
Example 2
(1) Mixing an octadecene solution of CdSe quantum dots with the concentration of 50mg/mL with a titanium isopropoxide solution, wherein the addition amount of the titanium isopropoxide is 5% of the volume of the quantum dot solution, and heating and stirring the mixture at 200 ℃ for 5min under an argon atmosphere to obtain a reacted solution;
(2) and (2) cooling the reacted liquid obtained in the step (1) to room temperature, mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, wherein the volume ratio of the reacted liquid to the toluene to the ethanol is 1:1:3, and performing centrifugal separation to obtain the titanium ion modified CdSe quantum dot.
Example 3
The embodiment provides a preparation method of a waterproof oxygen quantum dot, which comprises the following steps:
(1) mixing an octadecylene solution of InP quantum dots with the concentration of 20mg/mL with a tetrabutyl titanate solution, wherein the addition amount of tetrabutyl titanate is 1% of the volume of the quantum dot solution, and heating and stirring at 150 ℃ for reaction for 30min under an argon atmosphere to obtain a reacted solution;
(2) and (2) cooling the reacted liquid obtained in the step (1) to room temperature, mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, wherein the volume ratio of the reacted liquid to the toluene to the ethanol is 1:1:3, and performing centrifugal separation to obtain the titanium ion modified InP quantum dots.
Example 4
The embodiment provides a preparation method of a waterproof oxygen quantum dot, which comprises the following steps:
(1) CuInS with the concentration of 100mg/mL2Mixing an octadecylene solution of quantum dots with a tetraisopropyl titanate solution, wherein the addition amount of tetraisopropyl titanate is 0.5% of the volume of the quantum dot solution, and heating and stirring the mixture at 100 ℃ in an argon atmosphere for reacting for 60min to obtain a reacted solution;
(2) cooling the reacted liquid in the step (1) to room temperature, mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, wherein the volume ratio of the reacted liquid to the toluene to the ethanol is 1:1:3, and performing centrifugal separation to obtain the titanium ion modified CuInS2And (4) quantum dots.
Example 5
The embodiment provides a preparation method of a waterproof oxygen quantum dot, which comprises the following steps:
(1) mixing 200mg/mL CdTe quantum dot octadecylene solution with zirconium n-propoxide solution, wherein the addition of the zirconium n-propoxide is 0.5% of the volume of the quantum dot solution, and heating and stirring the mixture at 80 ℃ for reaction for 120min under the argon atmosphere to obtain reacted solution;
(2) and (2) cooling the reacted liquid obtained in the step (1) to room temperature, mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, wherein the volume ratio of the reacted liquid to the toluene to the ethanol is 1:1:3, and performing centrifugal separation to obtain the titanium ion modified CdTe quantum dot.
Example 6
The embodiment provides a preparation method of a waterproof oxygen quantum dot, which comprises the following steps:
(1) mixing an octadecylene solution of CdZnSSe quantum dots with the concentration of 1mg/mL with a n-butyl zirconium solution, wherein the addition amount of the n-propyl zirconium is 0.1 percent of the volume of the quantum dot solution, and heating and stirring the mixture at 150 ℃ for reaction for 300min under the argon atmosphere to obtain a reacted solution;
(2) and (2) cooling the reacted liquid obtained in the step (1) to room temperature, mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, wherein the volume ratio of the reacted liquid to the toluene to the ethanol is 1:1:3, and performing centrifugal separation to obtain the titanium ion modified CdZnSSe quantum dot.
The examples 1-6 and the original quantum dots used in each were subjected to aging tests by exposing the quantum dot samples to blue light for continuous irradiation, recording the quantum yields of the quantum dots at different times, and the results are shown in table 1, where table 1 is the residual quantum yield of the quantum dot samples after aging for 75 hours under blue light for continuous irradiation.
TABLE 1
| Primary quantum dots | Metal ion modified quantum dot | |
| Example 1 | 78.5％ | 92.1％ |
| Example 2 | 80.4％ | 91.4％ |
| Example 3 | 43.3％ | 58.7％ |
| Example 4 | 76.7％ | 88.2％ |
| Example 5 | 67.3％ | 76.2％ |
| Example 6 | 80.9％ | 88.5％ |
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The waterproof oxygen quantum dot is characterized in that metal ions are modified outside the quantum dot.
2. The water repellant oxygen quantum dot of claim 1, wherein the metal ions comprise titanium ions and/or zirconium ions.
3. The water repellent oxygen quantum dot according to claim 1, wherein the quantum dot comprises one or a combination of at least two of CdSe, CdTe, CdS, ZnSe, CdTe, CuInS, InP, CuInSe, or CdZnSSe, preferably CdSe.
4. A method for preparing the waterproof oxygen quantum dot as claimed in any one of claims 1 to 3, which comprises the following steps:
(1) mixing the quantum dot solution with the metal precursor solution, and heating and reacting under the atmosphere of protective gas to obtain a reacted solution;
(2) and (2) cooling the reacted liquid obtained in the step (1), and carrying out solid-liquid separation and purification to obtain the waterproof oxygen quantum dots.
5. The preparation method according to claim 4, wherein the concentration of the quantum dot solution in the step (1) is 1-200 mg/mL;
preferably, the solvent of the quantum dot solution in the step (1) is octadecene and/or liquid paraffin.
6. The method according to claim 4 or 5, wherein the metal precursor of step (1) comprises any one of titanium isopropoxide, tetrabutyl titanate, tetraisopropyl titanate, zirconium n-propoxide, or zirconium n-butoxide, or a combination of at least two thereof;
preferably, the addition amount of the metal precursor in the step (1) is 0.1-5% of the volume of the quantum dot solution.
7. The method according to any one of claims 4 to 6, wherein the temperature of the heating reaction in step (1) is 60 to 200 ℃;
preferably, the heating reaction time in the step (1) is 5-300 min;
preferably, the heating reaction of step (1) is carried out under stirring;
preferably, the protective gas in step (1) comprises any one or a combination of at least two of nitrogen, helium or argon.
8. The method according to any one of claims 4 to 7, wherein the cooling in step (2) is performed by cooling the cooled liquid to room temperature.
9. The production method according to any one of claims 4 to 8, wherein the solid-liquid separation and purification in step (2) comprises mixing the cooled post-reaction liquid with a mixed solution of toluene and ethanol, and centrifuging.
10. The method for preparing according to any one of claims 4 to 9, characterized in that it comprises the steps of:
(1) mixing a quantum dot solution with the concentration of 1-200 mg/mL with a metal precursor solution, wherein the addition amount of the metal precursor is 0.1-5% of the volume of the quantum dot solution, and heating and stirring at 60-200 ℃ for 5-300 min under the atmosphere of protective gas to react to obtain a reacted solution;
the solvent of the quantum dot solution is octadecene and/or liquid paraffin, and the metal precursor comprises any one or the combination of at least two of titanium isopropoxide, tetrabutyl titanate, tetraisopropyl titanate, zirconium n-propoxide or zirconium n-butoxide;
(2) and (2) cooling the reacted liquid in the step (1) to room temperature, mixing the cooled reacted liquid with a mixed solution of toluene and ethanol, and performing centrifugal separation to obtain the waterproof oxygen quantum dot.
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