Modified hollow glass bead as well as preparation method and application thereof

Abstract

The invention discloses a modified hollow glass bead and a preparation method and application thereof, and relates to the technical field of material modification.The modified hollow glass bead comprises a hollow glass bead carrier and semiconductor quantum dots loaded on the surface of the hollow glass bead carrier, and the semiconductor quantum dots pass through 1, 2, 3, 4-tetramethyl-1, 3-pentanediol monoisobutyrate. A 1, 2, 3-triazole structure is connected to the hollow glass carrier, and the semiconductor quantum dots are directionally arranged along the same direction. In the modified hollow glass bead provided by the invention, the hollow glass bead carrier is connected with the semiconductor quantum dots through the 1, 2, 3-triazole structure, so that the semiconductor quantum dots are not in direct contact with the carrier, the light response effect of the semiconductor quantum dots is conveniently exerted, and meanwhile, the semiconductor quantum dots arranged along the same direction not only have higher fluorescence efficiency, but also have higher fluorescence intensity. In addition, the surface defects are reduced, and the hydrophobicity of the modified hollow glass beads is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of material modification, and in particular to a modified hollow glass microsphere and a preparation method and application thereof. Background Art

[0002] Hollow glass microspheres have many advantages such as low thermal conductivity, hollow structure, low density, good insulation performance, high compressive strength, good chemical stability, and excellent wear resistance. They are often used as lightweight materials or packaging materials.

[0003] However, domestic hollow glass microspheres have some hydrophilic groups on their surface, which easily absorb moisture and harden when exposed to air, seriously affecting their subsequent use. However, hollow glass microspheres produced abroad can also maintain good dryness after long-term exposure to air. Therefore, it is necessary to modify the surface of domestic hollow glass microspheres to make them hydrophobic. Summary of the Invention

[0004] The main purpose of the present invention is to provide a modified hollow glass microsphere and its preparation method and application, aiming to solve the problem of poor hydrophobicity of hollow glass microspheres in the prior art.

[0005] To achieve the above objectives, the present invention proposes a modified hollow glass microsphere, comprising a hollow glass microsphere carrier and semiconductor quantum dots loaded on the surface of the hollow glass microsphere carrier, wherein the semiconductor quantum dots are connected to the hollow glass carrier through a 1,2,3-triazole structure, wherein the semiconductor quantum dots are directionally arranged in the same direction.

[0006] In one embodiment, the mass ratio of the hollow glass microsphere carrier to the semiconductor quantum dots is (3-5):1; and / or, The distance between the hollow glass microsphere carrier and the semiconductor quantum dots is 5 to 15 nm; and / or, The particle size of the hollow glass microsphere carrier is 50-100 μm; and / or, The semiconductor quantum dots include CdSe quantum dots and / or CdTe quantum dots.

[0007] In one embodiment, the semiconductor quantum dots include CdSe quantum dots: The surface of the hollow glass microsphere carrier has a silicon-oxygen-silicon bond, the surface of the CdSe quantum dot has a Cd-sulfur bond, and the 1,2,3-triazole structure is connected between the silicon-oxygen-silicon bond and the Cd-sulfur bond.

[0008] The present invention also provides a method for preparing modified hollow glass microspheres, comprising the following steps: S1. Providing a hollow glass microbead having a surface containing a hydroxyl group, mixing a silane compound containing a polycyclic alkynyl group and an alkoxy group, the hollow glass microbead having a surface containing a hydroxyl group, and a first solvent, so that the hydroxyl groups on the surface of the hollow glass microbead undergo a silanization reaction with the alkoxy groups in the silane compound to obtain a hollow glass microbead having a surface containing a polycyclic alkynyl group; S2. Providing a semiconductor quantum dot having thioglycolic acid on its surface, mixing the semiconductor quantum dot having thioglycolic acid on its surface, water, and a thiol compound containing an azide group under light-shielding conditions, and performing a ligand exchange reaction to obtain a semiconductor quantum dot having an azide group on its surface; S3, mixing the semiconductor quantum dots having azide groups on the surface, the hollow glass microbeads having polycyclic cycloalkyne groups on the surface, and a second solvent under light-shielding conditions, and performing a click chemistry reaction to obtain hollow modified glass microbeads having semiconductor quantum dots loaded on the surface; S4. Subjecting the hollow glass microbeads loaded with semiconductor quantum dots on the surface to electric field induction to direct the semiconductor quantum dots on the surface of the hollow glass microbeads in the same direction to obtain the modified hollow glass microbeads.

[0009] In one embodiment, in step S1, the step of providing a hollow glass microsphere having a surface containing hydroxyl groups comprises: The hollow glass microspheres are mixed with an alkaline solution to carry out a hydroxylation reaction to obtain hollow glass microspheres containing hydroxyl groups on the surface.

[0010] In one embodiment, the mass ratio of the hollow glass microspheres to the alkaline solution is 1:(2-3); and / or, The mass ratio of the hollow glass microspheres containing hydroxyl groups on the surface to the silane compound containing polycyclic cycloalkynyl groups and alkoxy groups is 1: (0.8-1.2); and / or, The first solvent comprises ethanol and / or water; and / or, The silanization reaction time is 12 to 24 hours; and / or, The temperature of the silanization reaction is 20-25° C.; and / or, The pH of the silanization reaction is 4 to 6; and / or, The silane compound containing a polycyclic cycloalkynyl group and an alkoxy group includes at least one of (8-(trimethoxysilyl)octyl)cyclooctyne, (6-(trimethoxysilyl)hexyl)cyclooctyne and (10-(trimethoxysilyl)decyl)cyclooctyne.

[0011] In one embodiment, in step S2: The mass ratio of the semiconductor quantum dots containing thioglycolic acid on the surface to the thiol compound containing an azide group is 1:(25-30); and / or, The thiol compound containing an azide group includes at least one of 11-azido-3,6,9-trioxaundecanethiol, 6-azidohexylthiol and 12-azidododecanethiol; and / or, The temperature of the ligand exchange reaction is 20-25° C.; and / or, The ligand exchange reaction time is 20 to 24 hours.

[0012] In one embodiment, in step S3: The mass ratio of the semiconductor quantum dots containing azide groups on the surface to the hollow glass microspheres containing polycyclic cycloalkyne groups on the surface is 1:(3-6); and / or, The second solvent comprises a phosphate buffer solution having a pH of 7 or water; and / or, The click chemistry reaction time is 4 to 8 hours; and / or, The temperature of the click chemistry reaction is 20-25°C.

[0013] In one embodiment, in step S4: The electric field strength induced by the electric field is 80-100 V / cm; and / or, The temperature induced by the electric field is 40-60° C.; and / or, The electric field induction time is 10 to 20 minutes.

[0014] The present invention also provides a use of the aforementioned modified hollow glass microspheres or the modified hollow glass microspheres prepared by the aforementioned method for preparing the modified hollow glass microspheres in light-emitting diodes.

[0015] In the technical solution of the present invention, the hollow glass microsphere carrier and the semiconductor quantum dots are connected through a 1,2,3-triazole structure, so that the semiconductor quantum dots do not directly contact the carrier, which facilitates the semiconductor quantum dots to exert their light response effect. At the same time, the semiconductor quantum dots arranged in the same direction not only have higher fluorescence efficiency, but also reduce surface defects and improve the hydrophobicity of the modified hollow glass microspheres.

[0016] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. Where the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased commercially. In addition, the meaning of "and / or" appearing in the full text includes three parallel schemes. Taking "A and / or B" as an example, it includes scheme A, or scheme B, or schemes that A and B meet at the same time. In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on the ability of ordinary technicians in this field to achieve. When the combination of technical solutions is contradictory or cannot be achieved, it should be considered that the combination of such technical solutions does not exist and is not within the scope of protection required by the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0018] Hollow glass microspheres have many advantages such as low thermal conductivity, hollow structure, low density, good insulation performance, high compressive strength, good chemical stability, and excellent wear resistance. They are often used as lightweight materials or packaging materials.

[0019] However, domestic hollow glass microspheres have some hydrophilic groups on their surface, which easily absorb moisture and harden when exposed to air, seriously affecting their subsequent use. However, hollow glass microspheres produced abroad can also maintain good dryness after long-term exposure to air. Therefore, it is necessary to modify the surface of domestic hollow glass microspheres to make them hydrophobic.

[0020] In view of this, the present invention provides a modified hollow glass microsphere, comprising a hollow glass microsphere carrier and semiconductor quantum dots loaded on the surface of the hollow glass microsphere carrier, wherein the semiconductor quantum dots are connected to the hollow glass carrier through a 1,2,3-triazole structure, wherein the semiconductor quantum dots are directionally arranged in the same direction.

[0021] In the technical solution of the present invention, the hollow glass microsphere carrier and the semiconductor quantum dots are connected through a 1,2,3-triazole structure, so that the semiconductor quantum dots do not directly contact the carrier, which facilitates the semiconductor quantum dots to exert their light response effect. At the same time, the semiconductor quantum dots arranged in the same direction not only have higher fluorescence efficiency, but also reduce surface defects and improve the hydrophobicity of the modified hollow glass microspheres.

[0022] In some embodiments, the mass ratio of the hollow glass microsphere carrier to the semiconductor quantum dots is (3-5):1. It is understood that the mass ratio of the hollow glass microsphere carrier to the semiconductor quantum dots can be 3:1, 4:1, or 5:1. The mass ratio within the above range can ensure that the semiconductor quantum dots are more evenly dispersed on the surface of the hollow glass microsphere carrier and are not easily aggregated.

[0023] In some embodiments, the distance between the hollow glass microsphere carrier and the semiconductor quantum dot is 5-15 nm. It is understood that the distance between the hollow glass microsphere carrier and the semiconductor quantum dot can be 5 nm, 10 nm, or 15 nm. The distance within the above range can ensure high fluorescence efficiency of the semiconductor quantum dot.

[0024] In some embodiments, the hollow glass microsphere carrier has a particle size of 50 to 100 μm. It is understood that the particle size of the hollow glass microsphere carrier can be 50 μm, 89 μm, or 100 μm. The particle size within the above range can ensure that it can better support the surface-grafted groups and semiconductor quantum dots.

[0025] In some embodiments, the semiconductor quantum dots include CdSe quantum dots and / or CdTe quantum dots. The fluorescence efficiency of the above two types of semiconductor quantum dots is relatively high. It should be noted that the fluorescence efficiency refers to the fluorescence quantum yield. Preferably, the semiconductor quantum dots include CdSe quantum dots: the surface of the hollow glass microsphere carrier has a silicon-oxygen-silicon bond, the surface of the CdSe quantum dots has a Cd-sulfur bond, and the 1,2,3-triazole structure is connected between the silicon-oxygen-silicon bond and the Cd-sulfur bond. This connection method stably expands the distance between the semiconductor quantum dots and the hollow glass microsphere carrier, so that it can be stably maintained between 5 and 15 nm. Under this structure, the fluorescence efficiency of the CdSe quantum dots is relatively high, and the modified hollow glass microspheres are relatively hydrophobic, and the mechanical strength is relatively good.

[0026] The present invention also provides a method for preparing modified hollow glass microspheres, comprising the following steps: S1. Providing a hollow glass microbead having a surface containing a hydroxyl group, mixing a silane compound containing a polycyclic alkynyl group and an alkoxy group, the hollow glass microbead having a surface containing a hydroxyl group, and a first solvent, so that the hydroxyl groups on the surface of the hollow glass microbead undergo a silanization reaction with the alkoxy groups in the silane compound to obtain a hollow glass microbead having a surface containing a polycyclic alkynyl group; S2. Providing a semiconductor quantum dot having thioglycolic acid on its surface, mixing the semiconductor quantum dot having thioglycolic acid on its surface, water, and a thiol compound containing an azide group under light-shielding conditions, and performing a ligand exchange reaction to obtain a semiconductor quantum dot having an azide group on its surface; S3, mixing the semiconductor quantum dots having azide groups on the surface, the hollow glass microbeads having polycyclic cycloalkyne groups on the surface, and a second solvent under light-shielding conditions, and performing a click chemistry reaction to obtain hollow modified glass microbeads having quantum dots loaded on the surface; S4. Subjecting the hollow glass microbeads loaded with semiconductor quantum dots on the surface to electric field induction to direct the semiconductor quantum dots on the surface of the hollow glass microbeads in the same direction to obtain the modified hollow glass microbeads.

[0027] In the technical solution of the present invention, in step S1, a silanization reaction is carried out between the hydroxyl groups on the surface of the hollow glass microspheres and the alkoxy groups in the silane compound, so that the surface of the hollow glass microspheres contains a multi-cycloalkynyl group, which provides a multi-cycloalkynyl site for the subsequent click chemistry reaction, facilitates the efficient coupling of the target molecule, and at the same time, the Si-O-Si bond formed by the silanization reaction has good thermal stability and chemical stability, thereby improving the durability of the material; in step S2, the original thioglycolic acid ligand on the surface of the semiconductor quantum dot is exchanged with the thiol compound through ligand exchange, that is, the thiol compound competitively replaces the original thioglycolic acid on the surface of the semiconductor quantum dot and forms a metal-thiol bond with the semiconductor quantum dot to firmly bind, at this time, the azide group in the thiol compound is at the end away from the semiconductor quantum dot, which is convenient for subsequent participation in the strain-promoted azide-alkyne cycloaddition reaction. reaction; in step S3, the stress-promoted electrode chemical reaction between the diversified alkynyl groups and the azide groups is used to combine the hollow glass microspheres and the semiconductor quantum dots with high speed, high accuracy and high specificity, so that there is a certain distance between the hollow glass microspheres and the semiconductor quantum dots and they can be firmly and stably combined, thereby improving the stability of the material in a complex environment, so that the hollow glass microspheres loaded with quantum dots on the surface have both good fluorescence efficiency and hydrophobicity; in step S4, an electric field is applied to the hollow glass microspheres loaded with quantum dots on the surface, and the dielectrophoresis effect or dipole orientation effect is used to make the quantum dots arranged in an orderly manner along the direction of the electric field, thereby obtaining a new functional material with directional optical behavior, and the directional arrangement enhances the luminous efficiency and directionality of the modified hollow glass microspheres, reduces self-absorption and non-uniform scattering, and improves the consistency between material batches.

[0028] In one embodiment, in step S1, providing hollow glass microspheres having surface hydroxyl groups includes mixing the hollow glass microspheres with an alkaline solution to undergo a hydroxylation reaction to obtain hollow glass microspheres having surface hydroxyl groups. By mixing the hollow glass microspheres with the alkaline solution, the alkaline solution etches the surface of the hollow glass microspheres, promoting a hydrolysis reaction on the glass surface, successfully introducing hydroxyl groups onto the surface of the hollow glass microspheres, and significantly increasing their surface activity.

[0029] In some embodiments, the mass ratio of the hollow glass microspheres to the alkaline solution is 1:(2-3). The mass ratio of the hollow glass microspheres to the alkaline solution can be 1:2, 1:2.5, or 1:3. Within the above range, the mass ratio can ensure that the surface of the hollow glass microspheres is etched and introduced with a large number of active hydroxyl groups without excessively increasing the roughness of the surface of the hollow glass microspheres.

[0030] In some embodiments, the mass ratio of the hollow glass microspheres containing hydroxyl groups on the surface to the silane compound containing polycyclic alkynyl groups and alkoxy groups is 1:(0.8-1.2). The mass ratio of the hollow glass microspheres containing hydroxyl groups on the surface to the silane compound containing polycyclic alkynyl groups and alkoxy groups can be 1:0.8, 1:1, or 1:2. Within the above-mentioned mass ratio range, the hydroxyl groups on the surface of the hollow glass microspheres can fully react with the alkoxy groups in the silane compound to form a silylation reaction, resulting in a larger number of available polycyclic alkynyl groups on the surface of the hollow glass microspheres.

[0031] In some embodiments, the first solvent includes ethanol and / or water. That is, the hollow glass microspheres containing hydroxyl groups on the surface and the silane compound can be dissolved or dispersed in ethanol or water, or in an aqueous solution of ethanol to facilitate the silanization reaction, preferably an aqueous solution of ethanol.

[0032] In some embodiments, the silanization reaction time is 12 to 24 hours; and / or the silanization reaction temperature is 20 to 25° C.; and / or the silanization reaction pH is 4 to 6. Simultaneously controlling the silanization reaction time, temperature, and pH within the aforementioned ranges can ensure that the hydroxyl groups on the surface of the hollow glass microspheres can fully react with the alkoxy groups in the silane compound to generate a silylation reaction, resulting in a larger number of available polycyclic alkynyl groups on the surface of the hollow glass microspheres.

[0033] In some embodiments, the silane compound containing a polycyclic cycloalkynyl group and an alkoxy group includes at least one of (8-(trimethoxysilyl)octyl)cyclooctyne, (6-(trimethoxysilyl)hexyl)cyclooctyne, and (10-(trimethoxysilyl)decyl)cyclooctyne. It is understood that the silane compound containing a polycyclic cycloalkynyl group and an alkoxy group may be any one of (8-(trimethoxysilyl)octyl)cyclooctyne, (6-(trimethoxysilyl)hexyl)cyclooctyne, and (10-(trimethoxysilyl)decyl)cyclooctyne, or two or more of (8-(trimethoxysilyl)octyl)cyclooctyne, (6-(trimethoxysilyl)hexyl)cyclooctyne, and (10-(trimethoxysilyl)decyl)cyclooctyne, all within the scope of protection of the present invention. The selection of the above-mentioned silane compound can provide a certain distance between the hollow glass microspheres and the semiconductor quantum dots, while providing better hydrophobicity and providing polycyclic cycloalkyne groups for subsequent click chemistry reactions.

[0034] In some embodiments, in step S2, the mass ratio of the semiconductor quantum dots containing thioglycolic acid on the surface to the thiol compound containing an azide group is 1:(25-30). It is understood that the mass ratio of the semiconductor quantum dots containing thioglycolic acid on the surface to the thiol compound containing an azide group can be 1:25, 1:27, or 1:30. Within the above range, the mass ratio can ensure that the thiol compound can fully replace all mercaptoethanol on the surface of the semiconductor quantum dots.

[0035] In some embodiments, in step S2, the thiol compound containing an azide group includes at least one of 11-azido-3,6,9-trioxaundecanethiol, 6-azidohexylthiol, and 12-azidododecanethiol. It is understood that the thiol compound containing an azide group can be any one of azido-3,6,9-trioxaundecanethiol, 6-azidohexylthiol, and 12-azidododecanethiol, or two or more of azido-3,6,9-trioxaundecanethiol, 6-azidohexylthiol, and 12-azidododecanethiol, all within the scope of protection of the present invention. The selection of the above thiol compounds can further provide a certain distance between the hollow glass microspheres and the semiconductor quantum dots, while also providing better hydrophobicity.

[0036] In some embodiments, in step S2, the ligand exchange reaction temperature is 20-25°C; and / or the ligand exchange reaction duration is 20-24 hours. Controlling the ligand exchange reaction temperature and duration within these ranges can ensure that the thiol compound fully replaces the mercaptoethanol on the surface of the semiconductor quantum dots.

[0037] In some embodiments, in step S3, the mass ratio of the semiconductor quantum dots containing azide groups on their surfaces to the hollow glass microbeads containing polycyclic cycloalkyne groups on their surfaces is 1:(3-6). The mass ratio of the semiconductor quantum dots containing azide groups on their surfaces to the hollow glass microbeads containing polycyclic cycloalkyne groups on their surfaces can be 1:3, 1:4, or 1:6. Within the above-mentioned mass ratio range, the quantum dots and hollow glass microbeads can be sufficiently bonded together through the click chemistry reaction between the azide groups and the polycyclic cycloalkyne groups, while preventing aggregation of the quantum dots due to an excess of semiconductor quantum dots, which could affect fluorescence efficiency.

[0038] In some embodiments, in step S3, the second solvent includes a phosphate buffer solution or water at a pH of 7. The second solvent is preferably a phosphate buffer solution (pH = 7), which can better promote click chemistry reactions.

[0039] In some embodiments, in step S3, the click chemistry reaction time is 4-8 hours; and / or the click chemistry reaction temperature is 20-25° C. Controlling the click chemistry reaction time and temperature within these ranges can ensure that the azide groups on the surface of the semiconductor quantum dots fully bind to the polycyclic cycloalkyne groups on the surface of the hollow glass microbeads.

[0040] In some embodiments, in step S4, the electric field intensity of the induced electric field is 80-100 V / cm; and / or the electric field induction temperature is 40-60°C; and / or the electric field induction duration is 10-20 minutes. Simultaneously controlling the electric field intensity, temperature, and duration of the induced electric field within the aforementioned ranges can ensure that the majority of semiconductor quantum dots loaded on the surface of the hollow glass microspheres are quickly aligned in the same direction, thereby improving luminous efficiency.

[0041] The present invention also provides the aforementioned modified hollow glass microspheres or modified hollow glass microspheres prepared by the aforementioned method for preparing the modified hollow glass microspheres for use in light-emitting diodes. Therefore, all the beneficial effects of the aforementioned modified hollow glass microspheres or the aforementioned method for preparing the modified hollow glass microspheres are achieved, and no further details are given here.

[0042] The technical solutions of the present invention are further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0043] Example 1 A modified hollow glass microsphere is prepared by the following steps: S1. Disperse hollow glass microspheres in ethanol, ultrasonically clean for 30 minutes to remove impurities, then wash three times with water, and dry to obtain cleaned hollow glass microspheres; add the hollow glass microspheres to 0.5 mol / L sodium hydroxide solution at a mass ratio of 1:3, stir at 80°C and 400 r / min for 1 hour, and then filter to obtain hollow glass microspheres containing hydroxyl groups on the surface; mix 50 mg of hollow glass microspheres containing hydroxyl groups on the surface, 5 mL of ethanol solution (ethanol: water volume ratio is 1:1), and 50 mg of (8-(trimethoxysilyl)octyl)cyclooctyne, adjust the pH value of the system to 4.5 with acetic acid, and carry out silane hydrolysis and condensation reaction by magnetic stirring at 20°C for a total reaction of 24 hours; then collect the solid phase by centrifugation, wash it alternately with ethanol and water three times, and dry it at 60°C to obtain hollow glass microspheres containing cyclooctyne on the surface; S2. A 10 mM aqueous solution of 11-azido-3,6,9-trioxaundecanethiol was mixed with a 1 mg / mL solution of CdSe quantum dots with thioglycolic acid ligands in the dark (volume ratio of 10:1), wherein the mass ratio of CdSe quantum dots containing thioglycolic acid on the surface to 11-azido-3,6,9-trioxaundecanethiol was 1:28, and then the mixture was stirred in the dark at 20°C for 24 hours, and unreacted 11-azido-3,6,9-trioxaundecanethiol was removed by dialysis to obtain CdSe quantum dots containing azide groups on the surface; S3. Add 50 mg of hollow glass microspheres containing cyclooctyne on the surface to 10 mL of phosphate buffer solution (pH = 7.4), and add 1 mg / mL of CdSe quantum dot solution containing azide groups on the surface under light-shielding conditions, wherein the mass ratio of hollow glass microspheres containing cyclooctyne on the surface to CdSe quantum dots containing azide groups on the surface is 5:1. Oscillate the reaction for 4 hours, collect the solid phase by centrifugation, and wash it alternately with ethanol and water three times to obtain hollow glass microspheres with CdSe quantum dots loaded on the surface; S4. Hollow glass microspheres loaded with CdSe quantum dots were mixed with cyclohexane to prepare a suspension with a concentration of 10 mg / mL. Two parallel copper electrodes connected to a DC power supply were immersed in the suspension (with a spacing of 1 cm). The initial voltage was adjusted to 100 V / cm. The voltage was applied at 40°C for 10 minutes. The power was then turned off and the liquid was quickly removed. The modified hollow glass microspheres were then dried in a low-temperature vacuum to obtain modified hollow glass microspheres.

[0044] Example 2 Compared with Example 1, Example 2 is different in that: In step S1, the mass ratio of the hollow glass microspheres to the sodium hydroxide solution is 1:2.

[0045] Example 3 Compared with Example 1, Example 3 is different in that: In step S1, the mass ratio of the hollow glass microspheres to the sodium hydroxide solution is 1:2.5.

[0046] Example 4 Compared with Example 1, Example 4 is different in that: In step S2, the mass ratio of the CdSe quantum dots containing thioglycolic acid on the surface to 11-azido-3,6,9-trioxaundecanethiol is 1:25.

[0047] Example 5 Compared with Example 1, Example 5 is different in that: In step S2, the mass ratio of the CdSe quantum dots containing thioglycolic acid on the surface to 11-azido-3,6,9-trioxaundecanethiol is 1:30.

[0048] Example 6 Compared with Example 1, Example 6 is different in that: In step S3, the mass ratio of the hollow glass microspheres containing cyclooctyne on the surface to the CdSe quantum dots containing azide groups on the surface is 3:1.

[0049] Example 7 Compared with Example 1, Example 7 is different in that: In step S3, the mass ratio of the hollow glass microspheres containing cyclooctyne on the surface to the CdSe quantum dots containing azide groups on the surface is 6:1.

[0050] Example 8 Compared with Example 1, Example 8 is different in that: In step S4 , the temperature at which the voltage is applied is 50° C.

[0051] Example 9 Compared with Example 1, Example 4 is different in that: In step S3 , the temperature at which the voltage is applied is 60° C.

[0052] Comparative Example 1 Comparative Example 1 provides a method for in-situ growth of CdSe quantum dots on the surface of hollow glass microspheres, comprising the following steps: 50 mg of hollow glass microspheres were dispersed in ethanol, ultrasonically cleaned for 30 min to remove impurities, then washed three times with water, and dried to obtain cleaned hollow glass microspheres; 50 mg of cleaned hollow glass microspheres were dispersed in 50 mL of octadecene, and 5 mmol of Cd(OAc)2·2H2O and 3 mmol of thioglycolic acid were added to form a uniform suspension. Subsequently, 5 mmol of NaHSe was gradually added at 150°C to start the nucleation process of CdSe quantum dots. Stirring was continued for 30 minutes, and the mixture was cooled to room temperature, centrifuged, and the solid phase was removed and low-temperature vacuum drying was performed to obtain hollow glass microspheres loaded with CdSe quantum dots.

[0053] Comparative Example 2 Comparative Example 2 is different from Example 1 in that: Step S1 is not performed.

[0054] Comparative Example 3 Comparative Example 3 is different from Example 1 in that: Step S4 is not performed.

[0055] Performance Testing The contact angle, fluorescence efficiency, mechanical properties and storage stability of the modified hollow glass microspheres finally prepared in Examples 1 to 9 and Comparative Examples 1 to 2 were tested. The testing methods are as follows: (1) Contact angle: The modified hollow glass microspheres were coated on a glass slide, deionized water was added at room temperature, and the static contact angle was recorded using a contact angle meter. (2) Fluorescence efficiency: The modified hollow glass microspheres were dispersed in toluene to prepare a solution with a concentration of 1 mg / mL. The absorption spectrum of the sample solution was measured using a UV-visible spectrophotometer to determine its maximum absorption wavelength. The emission spectrum of the sample was measured using a fluorescence spectrometer with λ_abs as the excitation wavelength, and the fluorescence intensity at the maximum emission wavelength was recorded. The relative quantum yield was calculated using a Rhodamine 6G standard sample as a reference. (3) Mechanical properties: The compressive strength of the modified hollow glass microspheres was tested using a universal material testing machine; (4) Storage stability: The modified hollow glass microspheres were sealed and stored at 25°C in the dark. The fluorescence efficiency was measured on the 0th and 30th day, and the loss rate of fluorescence efficiency after storage was calculated. The test results are shown in Table 1.

[0056] Table 1 Performance characteristics of the modified hollow glass microspheres in Examples 1 to 9 and Comparative Examples 1 to 2

[0057] As can be seen from Table 1, compared with the modified hollow glass microspheres prepared by the in situ method in Comparative Example 1, the modified hollow glass microspheres of the present invention have better hydrophobicity, fluorescence efficiency, compressive strength and storage stability. In addition, the fluorescence efficiency and hydrophobicity of the modified hollow glass microspheres induced by the electric field are higher, and the storage stability is also improved.

[0058] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Those skilled in the art will readily appreciate that the present invention is susceptible to various modifications and variations. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of the present invention.

Claims

1. A modified hollow glass microsphere, characterized in that: The invention comprises a hollow glass microsphere carrier and semiconductor quantum dots loaded on the surface of the hollow glass microsphere carrier, wherein the semiconductor quantum dots are connected to the hollow glass carrier through a 1,2,3-triazole structure, and the semiconductor quantum dots are directionally arranged in the same direction.

2. The modified hollow glass microsphere according to claim 1, wherein The mass ratio of the hollow glass microsphere carrier to the semiconductor quantum dots is (3-5):1; and / or, The distance between the hollow glass microsphere carrier and the semiconductor quantum dots is 5 to 15 nm; and / or, The particle size of the hollow glass microsphere carrier is 50 to 100 μm; and / or, The semiconductor quantum dots include CdSe quantum dots and / or CdTe quantum dots.

3. The modified hollow glass microsphere according to claim 1, wherein The semiconductor quantum dots include CdSe quantum dots: The surface of the hollow glass microsphere carrier has a silicon-oxygen-silicon bond, the surface of the CdSe quantum dot has a Cd-sulfur bond, and the 1,2,3-triazole structure is connected between the silicon-oxygen-silicon bond and the Cd-sulfur bond.

4. A method for preparing the modified hollow glass microspheres according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1. Providing a hollow glass microbead having a surface containing a hydroxyl group, mixing a silane compound containing a polycyclic alkynyl group and an alkoxy group, the hollow glass microbead having a surface containing a hydroxyl group, and a first solvent, so that the hydroxyl groups on the surface of the hollow glass microbead undergo a silanization reaction with the alkoxy groups in the silane compound to obtain a hollow glass microbead having a surface containing a polycyclic alkynyl group; S2. Providing a semiconductor quantum dot having thioglycolic acid on its surface, mixing the semiconductor quantum dot having thioglycolic acid on its surface, water, and a thiol compound containing an azide group under light-shielding conditions, and performing a ligand exchange reaction to obtain a semiconductor quantum dot having an azide group on its surface; S3, mixing the semiconductor quantum dots having azide groups on the surface, the hollow glass microbeads having polycyclic cycloalkyne groups on the surface, and a second solvent under light-shielding conditions, and performing a click chemistry reaction to obtain hollow modified glass microbeads having semiconductor quantum dots loaded on the surface; S4. Subjecting the hollow glass microbeads loaded with semiconductor quantum dots on the surface to electric field induction to direct the semiconductor quantum dots on the surface of the hollow glass microbeads in the same direction to obtain the modified hollow glass microbeads.

5. The method for preparing the modified hollow glass microspheres according to claim 4, wherein: In step S1, the step of providing a hollow glass microsphere having a surface containing hydroxyl groups comprises: The hollow glass microspheres are mixed with an alkaline solution to carry out a hydroxylation reaction to obtain hollow glass microspheres containing hydroxyl groups on the surface.

6. The method for preparing the modified hollow glass microspheres according to claim 5, wherein: The mass ratio of the hollow glass microspheres to the alkaline solution is 1:(2-3); and / or, The mass ratio of the hollow glass microspheres containing hydroxyl groups on the surface to the silane compound containing polycyclic cycloalkynyl groups and alkoxy groups is 1:(0.8-1.2); and / or, The first solvent comprises ethanol and / or water; and / or, The silanization reaction time is 12 to 24 hours; and / or, The temperature of the silanization reaction is 20-25° C.; and / or, The pH of the silanization reaction is 4 to 6; and / or, The silane compound containing a polycyclic cycloalkynyl group and an alkoxy group includes at least one of (8-(trimethoxysilyl)octyl)cyclooctyne, (6-(trimethoxysilyl)hexyl)cyclooctyne and (10-(trimethoxysilyl)decyl)cyclooctyne.

7. The method for preparing the modified hollow glass microspheres according to claim 4, wherein: In step S2: The mass ratio of the semiconductor quantum dots containing thioglycolic acid on the surface to the thiol compound containing an azide group is 1:(25-30); and / or, The thiol compound containing an azide group includes at least one of 11-azido-3,6,9-trioxaundecanethiol, 6-azidohexylthiol and 12-azidododecanethiol; and / or, The temperature of the ligand exchange reaction is 20-25° C.; and / or, The ligand exchange reaction time is 20 to 24 hours.

8. The method for preparing the modified hollow glass microspheres according to claim 4, wherein: In step S3: The mass ratio of the semiconductor quantum dots containing azide groups on the surface to the hollow glass microspheres containing polycyclic cycloalkyne groups on the surface is 1:(3-6); and / or, The second solvent comprises a phosphate buffer solution having a pH of 7 or water; and / or, The click chemistry reaction time is 4 to 8 hours; and / or, The temperature of the click chemistry reaction is 20-25°C.

9. The method for preparing the modified hollow glass microspheres according to claim 4, wherein: In step S4: The electric field strength induced by the electric field is 80 to 100 V / cm; and / or, The temperature induced by the electric field is 40 to 60° C.; and / or, The electric field induction time is 10 to 20 minutes.

10. Use of the modified hollow glass microspheres according to any one of claims 1 to 3 or the modified hollow glass microspheres prepared by the preparation method of the modified hollow glass microspheres according to any one of claims 4 to 9 in light-emitting diodes.

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