WO2020063253A1 - 复合材料及其制备方法和应用 - Google Patents

复合材料及其制备方法和应用 Download PDF

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WO2020063253A1
WO2020063253A1 PCT/CN2019/103583 CN2019103583W WO2020063253A1 WO 2020063253 A1 WO2020063253 A1 WO 2020063253A1 CN 2019103583 W CN2019103583 W CN 2019103583W WO 2020063253 A1 WO2020063253 A1 WO 2020063253A1
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silica
quantum dot
coated
composite material
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聂志文
杨一行
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TCL Corp
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/65—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing carbon
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/70—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing phosphorus
    • C09K11/701—Chalcogenides
    • C09K11/703—Chalcogenides with zinc or cadmium
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    • C09K11/88—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present application relates to the technical field of nanomaterials, and in particular, to a composite material, a preparation method and application thereof.
  • a quantum dot is a semiconductor nanoparticle with a particle radius smaller than or close to the exciton Bohr radius, usually composed of II-VI or III-V elements. After the quantum dots are excited by external light or electricity, the excited electrons transition to lower energy levels, radiating energy in the form of light energy, emitting fluorescence. Quantum dots have the advantages of simple preparation, narrow half-peak width, small particles without scattering loss, high luminous efficiency, and wide spectral coverage. They have broad application prospects in the fields of new display, lighting and biomarkers.
  • the problem that needs to be solved is their stability.
  • the quantum dots themselves have a small size distribution, most of which are below 10 nm, and the specific surface area is very large. They are very susceptible to environmental factors in the process of preparation and use. For example, the quantum dots are exposed to the air for a long time, and the contact of water and oxygen in the air will cause a large number of defects on the surface of the quantum dots, thereby greatly reducing their luminous efficiency and service life.
  • the problem of the poor stability of quantum dots has greatly limited their widespread use.
  • the most commonly used method to improve the stability of quantum dots is to use polymer or silica for coating, but these methods generally have some disadvantages, such as increasing the size of the quantum dots, damaging the surface of the quantum dots, and causing them to emit light. Reduced efficiency.
  • One of the objectives of the embodiments of the present application is to provide a composite material, a preparation method and application thereof, which are aimed at solving the technical problems of poor stability and low luminous efficiency of existing quantum dots.
  • a composite material includes a silica-coated quantum dot and a graphene nanosheet bonded to a surface of the silica-coated quantum dot; wherein, the silica The coated quantum dot includes a quantum dot and a silicon dioxide layer coated on the surface of the quantum dot, and the graphene nanosheet and the silicon dioxide layer pass through (O-) 3 Si-R 1 -NHCO-R 3 -CONH-R 2 -Si (O-) 3 or (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (O-) 3 combined, R 1 , R 2 , R 4 , R 5 is independently selected from a hydrocarbon group or a hydrocarbon-based derivative, and R 3 is selected from a hydrocarbon group, a hydrocarbon-based derivative, an aryl group, or an aryl derivative.
  • a method for preparing a composite material including the following steps:
  • the silica-coated quantum dot comprising a quantum dot and a silica layer coated on a surface of the quantum dot, the surface of the silica layer being combined with a first modifier
  • the first modifier is (O-) 3 Si-R 1 -NH 2 or (O-) 3 Si-R 1 -NHCO-R 3 -COOH, wherein R 1 is selected from a hydrocarbon group or a hydrocarbon-based derivative, and R 3 selected from hydrocarbyl, hydrocarbyl derivative, aryl or aryl derivative;
  • a graphene nanosheet is provided, and a surface of the graphene nanosheet is bound with a second modifier, and the second modifier is (O-) 3 Si-R 2 -NHCO-R 3 -COOH or (O-) 3 Si- R 2 -NH 2 , wherein R 2 is selected from a hydrocarbon group or a hydrocarbon group derivative,
  • the second modifier when the first modifier is (O-) 3 Si-R 1 -NH 2 , the second modifier is (O-) 3 Si-R 2 -NHCO-R 3 -COOH; when the first modifier is When the agent is (O-) 3 Si-R 1 -NHCO-R 3 -COOH, the second modifier is (O-) 3 Si-R 2 -NH 2 .
  • Another method for preparing a composite material includes the following steps:
  • Providing a silica-coated quantum dot the silica-coated quantum dot comprising a quantum dot and a silica layer coated on a surface of the quantum dot, the surface of the silica layer being combined with a third modifier,
  • Graphene nanosheets are provided.
  • an application of a composite material is provided, and the above-mentioned composite material of the present application or the composite material obtained by the above-mentioned preparation method is used as a light-emitting layer material of a quantum dot light-emitting diode.
  • the beneficial effects of the composite materials provided by the embodiments of the present application are as follows:
  • the graphene nanosheets not only have superior water / oxygen blocking ability, but also can effectively prevent water / oxygen from eroding the quantum dots, thereby preventing external environment from affecting
  • the irreversible effect of the quantum dots and the graphene nanosheets also have excellent thermal conductivity, which can improve the thermal stability of the composite material;
  • the graphene nanosheets are in direct contact with the quantum dots, they will cause quantum dot fluorescence bursts.
  • the defects can be eliminated, and the coating of the quantum dots on the surface of the silicon dioxide layer can effectively prevent the graphene nanosheets from directly contacting the quantum dots.
  • the silicon dioxide layer can further improve the stability of the quantum dots. Therefore, the unique structure of the composite material fully exerts the excellent performance of each component. Through the synergistic effect of the silica layer and the graphene nanosheets, the stability of the quantum dots can be further improved without affecting the inherent optical properties of the quantum dots. Performance, thereby improving luminous efficiency.
  • FIG. 1 is a schematic diagram of a composite material provided by an embodiment of the present application.
  • FIG. 2 is a composite material in which a graphene nanosheet and a silica layer provided by an embodiment of the present application are combined with (O-) 3 Si-R 1 -NHCO-R 3 -CONH-R 2 -Si (O-) 3 Schematic diagram of the general structure;
  • FIG. 3 is a composite material of a graphene nanosheet and a silicon dioxide layer provided by an embodiment of the present application through (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (O-) 3 Schematic diagram of the general structure;
  • FIG. 4 is a schematic flowchart of a method for preparing a composite material according to an embodiment of the present application
  • FIG. 5 is a schematic flowchart of a method for preparing a composite material according to an embodiment of the present application.
  • Some embodiments of the present application provide a composite material including a silica-coated quantum dot and a graphene nanosheet bonded to a surface of the silica-coated quantum dot; wherein the dioxide is The silicon-coated quantum dot includes a quantum dot and a silicon dioxide layer coated on the surface of the quantum dot, and the graphene nanosheet and the silicon dioxide layer pass through (O-) 3 Si-R 1 -NHCO- R 3 -CONH-R 2 -Si (O-) 3 or (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (O-) 3 combined, R 1 , R 2 , R 4 , R 5 is independently selected from a hydrocarbon group or a hydrocarbon-based derivative, and R 3 is selected from a hydrocarbon group, a hydrocarbon-based derivative, an aryl group, or an aryl derivative.
  • the composite material provided in the embodiment of the present application is composed of a quantum dot located inside, a silica layer covering the surface of the quantum dot, and a graphene nanosheet combined on the outer surface of the silica layer.
  • the surface of the quantum dot can be directly A silicon dioxide layer is formed (that is, a silica-coated quantum dot), but the silicon dioxide layer cannot be directly connected to the graphene nanosheets.
  • the (O-) 3 Si-R 1 -NHCO-R 3 -CONH-R 2 -Si (O-) 3 or (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (O-) 3 effectively connects the silicon dioxide layer with the graphene nanosheets, thereby forming the
  • the composite materials of the embodiments are applied; on the one hand, the graphene nanosheets not only have superior water / oxygen blocking ability, but can effectively block the erosion of quantum dots by water / oxygen, thereby avoiding the irreversible influence of the external environment on the quantum dots in the composite material Moreover, the graphene nanosheets also have excellent thermal conductivity, which can improve the thermal stability of the composite material.
  • the graphene nanosheets are in direct contact with the quantum dots, they will cause the defect of quantum dot fluorescence quenching.
  • the silicon oxide layer can be coated on the surface of the quantum dots.
  • Graphene nano-sheets avoid direct contact with the quantum dot, while the silicon dioxide layer may further enhance the stability of the quantum dots. Therefore, the unique structure of the composite material fully exerts the excellent performance of each component. Through the synergistic effect of the silica layer and the graphene nanosheets, the stability of the quantum dots can be further improved without affecting the inherent optical properties of the quantum dots. Performance, thereby improving luminous efficiency.
  • 11 is a quantum dot
  • 12 is a silicon dioxide layer
  • 13 is a graphene nanosheet; the schematic diagrams of the general structure of the two composite materials are shown in Figures 2 and 3, respectively.
  • the composite material may be "graphene nanosheets (O-) 3 Si- R 1 -NHCO-R 3 -CONH-R 2 -Si (O-) 3 silica-coated quantum dots "may also be” silica-coated quantum dots (O-) 3 Si-R 1 -NHCO -R 3 -CONH-R 2 -Si (O-) 3 graphene nanosheets "; because the structure of the connection site is symmetrical, both connection methods of silica-coated quantum dots and graphene nanosheets can be used A general representation shown in FIG. 2.
  • the composite material can be "graphene nanosheets (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (O-) 3 silica-coated quantum dots "may also be” silica-coated quantum dots (O-) 3 Si-R 4 -SCH 2 CH 2- R 5 -Si (O-) 3 graphene nanosheets "; due to the asymmetric structure of the connection site, the two connection methods of silica-coated quantum dots and graphene nanosheets are shown in Figures 3a and 3b, respectively.
  • the quantum dots include but are not limited to group II-VI quantum dots, group III-V quantum dots, group IV-VI compounds, group IV compounds, and I-III- At least one of Group VI quantum dots.
  • Quantum dots can be single-core quantum dots or core-shell quantum dots.
  • the thickness of the silica layer is 2-20 nm; if the thickness of the silica layer is too small, the stability of the quantum dots is insufficient, such as dioxide If the thickness of the silicon layer is too thick, the light-emitting performance of the quantum dots will be affected; therefore, the combined effect of the stability and light-emitting properties of the quantum dots will be the best in this thickness range.
  • the size of the graphene nanoplatelets is 2-20 nm.
  • different sizes of graphene nanosheets and silica-coated quantum dots can exist in different ways. Their relative sizes are different, and their coating effects are different.
  • one (eg, two or more) silica-coated quantum dots can be connected to one graphene nanosheet; when the size of graphene is moderate, such as 5-10nm, one silica-coated quantum dot There will be 2-3 graphene nanosheets on the surface; when the size of graphene is small, such as 2-5nm, there will be more (such as 4 or more) graphene nanosheets on the surface of a silica-coated quantum dot. .
  • the graphene nanosheets and the silica layer pass through (O-) 3 Si-R 1 -NHCO-R 3 -CONH-R 2- Si (O-) 3 is bonded, and R 1 and R 2 are each independently selected from a hydrocarbon group having 2 to 20 carbon atoms or a hydrocarbon group derivative having 2 to 20 carbon atoms, and R 3 is selected from 2 to 20 carbon atoms A hydrocarbon group, a hydrocarbon-based derivative having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl derivative having 6 to 20 carbon atoms.
  • R 1 and R 2 are independently selected from -CH 2 CH 2- , -CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 NHCH 2 CH Any of 2- , -CH 2 CH 2 CH 2 NHCH 2 CH 2 -and -CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2- ;
  • R 3 is selected from -CH 2 CH 2- , -CH 2 CH 2 CH 2- , Any of them.
  • the graphene nanosheets and the silica layer pass through (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si ( O-) 3 is bonded, and R 4 and R 5 are each independently selected from a hydrocarbon group having 2 to 20 carbon atoms or a hydrocarbon group derivative having 2 to 20 carbon atoms. In one embodiment, R 4 and R 5 are independently selected from -CH 2 CH 2 -or -CH 2 CH 2 CH 2- .
  • an embodiment of the present application provides a method for preparing a composite material. As shown in FIG. 4, the method includes the following steps:
  • the silica-coated quantum dot includes a quantum dot and a silica layer coated on a surface of the quantum dot.
  • the surface of the silica layer is combined with a first modification.
  • the first modifier is (O-) 3 Si-R 1 -NH 2 or (O-) 3 Si-R 1 -NHCO-R 3 -COOH, wherein R 1 is selected from a hydrocarbon group or a hydrocarbon group derivative R 3 is selected from a hydrocarbyl group, a hydrocarbyl derivative, an aryl group or an aryl derivative;
  • S02 Provide graphene nanosheets, wherein the surface of the graphene nanosheets is bound with a second modifier, and the second modifier is (O-) 3 Si-R 2 -NHCO-R 3 -COOH or (O-) 3 Si-R 2 -NH 2 , wherein R 2 is selected from a hydrocarbon group or a hydrocarbon group derivative;
  • the second modifier when the first modifier is (O-) 3 Si-R 1 -NH 2 , the second modifier is (O-) 3 Si-R 2 -NHCO-R 3 -COOH; when the first modifier is When the agent is (O-) 3 Si-R 1 -NHCO-R 3 -COOH, the second modifier is (O-) 3 Si-R 2 -NH 2 .
  • the method for preparing a composite material according to the embodiment of the present application is simple, safe, and easy to operate.
  • the surface of the silica-coated quantum dots and the surface of the graphene nanosheets are modified respectively, so that each surface is connected with a modifier that can react with each other.
  • (O-) 3 Si-R 1 -NHCO-R 3 -CONH-R 2 -Si (O-) 3 is formed by the reaction of the surface-attached modifier, and the silica-coated quantum dots are connected to the graphene nanosheets.
  • the first modifier when the first modifier is (O-) 3 Si-R 1 -NH 2 , the first modifier is selected from a silane coupling agent having an amino group, and the second modifier is selected A modifier obtained by a condensation reaction between a silane coupling agent having an amino group and an acid anhydride. That is, the first modifier is selected from a silane coupling agent having an amino group (ie, an aminosilane coupling agent).
  • the process of modifying the quantum dots with silica coating may include: directly using a silane coupler with an amino group.
  • a crosslinking agent performs amination modification of the silica-coated quantum dots to obtain "silica-coated quantum dots (O-) 3 Si-R 1 -NH 2 ".
  • the second modifier is selected from the modifiers obtained by the condensation reaction of an amino-containing silane coupling agent and an acid anhydride.
  • the process of modifying the graphene nanosheets may include: firstly using an amino-containing silane coupling agent to modify the graphite alkenyl amination nanosheet-modified, and then reacted with an acid anhydride, to give "a graphene nanosheet - (O-) 3 Si-R 2 -NHCO-R 3 -COOH".
  • the second modifier is (O-) 3 Si-R 2 -NH 2
  • the second modifier is selected from a silane coupling agent having an amino group
  • the first modifier is selected from an amino group-containing coupling agent.
  • Modifier obtained by condensation reaction of silane coupling agent and acid anhydride That is, the first modifier is selected from modifiers obtained by the condensation reaction of an amino-containing silane coupling agent (ie, an aminosilane coupling agent) and an acid anhydride.
  • the process of modifying the silica-coated quantum dots by modification may include: First, the silicon oxide-coated quantum dots were aminated with an amino-containing silane coupling agent, and then reacted with an acid anhydride to obtain "silica-coated quantum dots (O-) 3 Si-R 1 -NHCO-R 3 -COOH ".
  • the second modifier is selected from a silane coupling agent with an amino group.
  • the process of modifying the graphene nanosheets may include: directly using an amino group-containing silane coupling agent to perform amination modification on the graphene nanosheets. "H 2 NR 2 -Si (O-) 3 -graphene nanosheets" was produced.
  • the amino-containing silane coupling agent is specifically selected from at least one of a monoaminosilane coupling agent, a bisaminosilane coupling agent, and a triaminosilane coupling agent.
  • the aminosilane coupling agent is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminopropyltriethoxy Based silane.
  • the acid anhydride is selected from the group consisting of trimellitic anhydride, succinic anhydride, tetrachlorophthalic anhydride, cyclopentanedioic dianhydride, tetrahydrophthalic anhydride, phthalic anhydride, and diphenyl ether tetracarboxylic dianhydride.
  • R 1 and R 2 are a hydrocarbon group or a hydrocarbon derivative in a silane coupling agent having an amino group
  • R 3 is a hydrocarbon group, a hydrocarbon group derivative, an aryl group, or an aryl derivative in an acid anhydride.
  • R 1 and R 2 are independently selected from a hydrocarbon group having 2 to 20 carbon atoms or a hydrocarbon group derivative having 2 to 20 carbon atoms, and R 3 is selected from 2 to 20 carbon atoms.
  • R 1 and R 2 are independently selected from -CH 2 CH 2- , -CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 NHCH 2 CH Any of 2- , -CH 2 CH 2 CH 2 NHCH 2 CH 2 -and -CH 2 CH 2 CH 2 NHCH 2 CH 2 CH 2- ;
  • R 3 is selected from -CH 2 CH 2- , -CH 2 CH 2 CH 2- , Any of them.
  • the specific process of the amination modification of the graphene nanosheets or silica-coated quantum dots is: (1) dispersing the graphene nanosheets or silica-coated quantum dots In a polar solvent, a graphene nanosheet or a silica-coated quantum dot solution is formed; (2) At room temperature, an amino-containing silane couple is added to the graphene nanosheet or the silica-coated quantum dot composite solution. The catalyst and catalyst are reacted at 40 to 150 ° C for 20min to 24h. After the reaction is completed, the surface aminated graphene nanosheets or silica-coated quantum dots can be obtained by washing and drying with water. .
  • the polar solvent includes at least one of water, ethanol, methanol, glycerol, propylene glycol, acetonitrile, propanol, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, and the like;
  • the catalyst includes ammonia, At least one of ammonia, dimethylamine, diethylamine, trimethylamine, triethylamine, pyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrat-butylammonium hydroxide, etc .; the catalyst is in a mixed solution
  • the volume concentration is 0.1 to 100 ml / L; the volume concentration of the amino-containing silane coupling agent in the mixed solution is 0.1 to 50 ml / ml.
  • the specific process of carboxylation modification of the graphene nanosheets or silica-coated quantum dots includes: (1) the surface-modified graphene nanosheets or The silica-coated quantum dots are dispersed in a polar solvent to form a surface-aminated graphene nanosheet or a silica-coated quantum dot solution; (2) at room temperature, the graphite is aminated to the surface It is easy to add acid anhydride to ene nanosheets or silica-coated quantum dots, and react at room temperature for 20min to 24h. After the reaction is completed, the surface carboxylated modified graphene nanosheets can be obtained after washing and drying with water. Or silica-coated quantum dots.
  • the polar solvent includes water, ethanol, methanol, glycerin, propylene glycol, acetonitrile, propanol, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, and the like.
  • the mass ratio of the acid anhydride to the surface aminated graphene nanosheets or silica-coated quantum dots is 0.01 to 10: 1.
  • the method for preparing the silica-coated quantum dots includes the following steps: mixing a perhydropolysilazane solution and a quantum dot solution to form a silicon dioxide layer on the surface of the quantum dots.
  • the preparation process of traditional silica-coated quantum dots requires water or ammonia or other catalyst reagents. Because the quantum dots have a large specific surface area, these added water, ammonia or catalysts will reduce the fluorescence production of the quantum dots to a certain extent. rate.
  • the preparation of the silica-coated quantum dots in the embodiments of the present application is beneficial to the rapid hydrolysis and oxidation of perhydropolysilazane at low temperatures, thereby forming a dense silica layer on the surface of the quantum dots. This method can effectively avoid It is necessary to use ammonia or catalyst in the conventional coating process, which will irreversibly affect the quantum dots.
  • the preparation of the silica-coated quantum dots in this embodiment includes: (1) dispersing quantum dots in a non-polar solvent to form a quantum dot solution; (2) dispersing perhydropolysilazane in an electrode In a solvent, a sesquiperhydropolysilazane solution is formed; (2) At room temperature, a perhydropolysilazane solution is added to the quantum dot solution described in step (1) above, and the reaction is performed at room temperature. ⁇ 24h, you can get the quantum dots coated with silica;
  • the mass ratio of the perhydropolysilazane to the quantum dots is 0.01 to 10: 1, and the concentration of the quantum dots in the non-polar solvent is 0.01 to 300 mg / ml.
  • the volume ratio of the solvent to the non-polar solvent is 0.1 to 100: 1.
  • the above polar solvents include hexane, cyclohexane, toluene, chlorobenzene, diethyl ether, butyl ether, tetrahydrofuran, 1,4-dioxane, acetone, cyclohexanone, methyl isobutyl ketone, and ethylene glycol di Diethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl ether;
  • step S03 the graphene nanosheets bound with the second modifier on the surface and the silica-coated quantum dots bound with the first modifier on the surface are mixed to make the silica (O-) 3 Si-R 1 -NHCO-R 3 -CONH-R 2 -formed between the coated quantum dot and the graphene nanosheet by the reaction between the first modifier and the second modifier
  • the step of bonding Si (O-) 3 includes: under acidic conditions and under conditions of a first initiator, combining the graphene nanosheet with the second modifier on the surface and the first modifier with the surface
  • the silica-coated quantum dots are mixed and subjected to a condensation reaction to obtain the composite material.
  • the first initiator is selected from at least one of carbodiimide (EDC) and N-hydroxysuccinimide (NHS); in the amide condensation reaction, EDC or NHS is used as an activating agent for the carboxyl group. Or NHS can improve the coupling efficiency of amino groups with carboxyl groups. When the molar ratio of EDC and NHS is 1: 1, the amide condensation reaction efficiency is the highest. Furthermore, the pH of the acidic condition is 4-7.
  • the pH of the silica-coated quantum dot solution bound with the first modifier on the surface is adjusted to 4-7, and then a graphene nanosheet solution bound with the second modifier on the surface is added.
  • the amide bond is recombined.
  • the pH of the graphene nanosheet solution bound to the second modifier on the surface is adjusted to 4-7, and then a silica-coated quantum dot solution bound to the first modifier is added.
  • the amide bond is compounded, and the composite material can be prepared.
  • An embodiment of the present application also provides a method for preparing a composite material. As shown in FIG. 5, the method includes the following steps:
  • T01 Provide a silica-coated quantum dot.
  • the silica-coated quantum dot includes a quantum dot and a silicon dioxide layer coated on the surface of the quantum dot.
  • the surface of the silicon dioxide layer is combined with a third modification.
  • T03 mixing graphene nanosheets with the fourth modifier on the surface and silica-coated quantum dots with the third modifier on the surface, so that the silica-coated quantum dots and the graphene are mixed (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (O-) 3 formed by reacting nanosheets with the third modifier and the fourth modifier to obtain a composite material ;
  • the method for preparing a composite material according to the embodiment of the present application is simple, safe, and easy to operate.
  • the surface of the silica-coated quantum dots and the surface of the graphene nanosheets are modified respectively, so that each surface is connected with a modifier that can react with each other.
  • (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (O-) 3 is formed by the reaction of the surface-attached modifier, and the silica-coated quantum dots and the graphene nanosheets are connected together.
  • a composite material with a structure unique to the embodiment of the present application is obtained.
  • the third modifier is (O-) 3 Si-R 4 -SH
  • the third modifier is selected from a silane coupling agent having a mercapto group
  • the fourth modifier is selected from Vinyl-containing silane coupling agent. That is, the third modifier is selected from a thiol coupling agent with a mercapto group (ie, a thiol silane coupling agent).
  • the process of modifying the quantum dots with silica coating may include: directly using a silane couple with a mercapto group.
  • the cross-linking agent performs thiolization modification on the silica-coated quantum dots to obtain "silica-coated quantum dots (O-) 3 Si-R 4 -SH".
  • the fourth modifier is selected from a silane coupling agent with a vinyl group.
  • the fourth modifier is (O-) 3 Si-R 4 -SH
  • the fourth modifier is selected from a mercapto-containing silane coupling agent
  • the third modifier is selected from a vinyl group A silane coupling agent. That is, the third modifier is selected from a vinyl-containing silane coupling agent (that is, a vinyl silane coupling agent).
  • the fourth modifier is selected from a silane coupling agent with a mercapto group.
  • the process of modifying the graphene nanosheets may include directly thiolating the graphene nanosheets with a silane coupling agent with a mercapto group.
  • Graphene nano (O-) 3 Si-R 4 -SH was formed.
  • the above-mentioned mercapto-containing silane coupling agent is selected from at least one of ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane;
  • the vinyl-containing silane coupling agent is selected from vinyltrimethoxy Silane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri ( ⁇ -methoxyethoxy) silane, vinyltri-tert-butoxysilane, vinyltri-tert-butylperoxysilane And at least one of vinyl triacetoxysilane.
  • R 4 is a hydrocarbyl group or a hydrocarbyl derivative in a silane coupling agent with a mercapto group, and may specifically be a hydrocarbyl or hydrocarbyl derivative with a carbon number of 2-20;
  • R 5 is a silane coupling agent with a vinyl group
  • the hydrocarbyl or hydrocarbyl derivative may be a hydrocarbyl or hydrocarbyl derivative having 2 to 20 carbon atoms.
  • R 4 and R 5 are independently selected from -CH 2 CH 2 -or -CH 2 CH 2 CH 2- .
  • the specific process of thiolization modification of graphene nanosheets or silica-coated quantum dots is: (1) graphene nanosheets or silica-coated quantum dots Dispersed in polar solvents to form graphene nanosheets or silica-coated quantum dot solutions; (2) At room temperature, add mercapto-containing silane couples to the above graphene nanosheets or silica-coated quantum dot solutions. After the reaction, the mixture is reacted at 40 to 150 ° C. for 20 minutes to 24 hours. After the reaction is completed, the surface is mercapto-modified graphene nanosheets or silica-coated quantum dots can be obtained after washing and drying with water.
  • the above polar solvent includes at least one of water, ethanol, methanol, glycerol, propylene glycol, acetonitrile, propanol, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, and the like; a mercapto-containing silane coupling agent in a mixed solution
  • the volume concentration is 0.1-50ml / ml.
  • the vinylation modification of graphene nanosheets or silica-coated quantum dots is as follows: (1) graphene nanosheets or silica-coated quantum dots The dots are dispersed in a polar solvent to form a graphene nanosheet or a silica-coated quantum dot solution; (2) At room temperature, a vinyl group is added to the graphene nanosheet or the silica-coated quantum dot solution. A silane coupling agent is reacted at 40 to 150 ° C for 20 minutes to 24 hours. After the reaction is completed, the surface is mercapto-modified graphene nanosheets or silica-coated quantum dots can be obtained after washing and drying with water.
  • the polar solvents include water, ethanol, methanol, glycerol, propylene glycol, acetonitrile, propanol, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, and the like.
  • the graphene nanosheets bound with the fourth modifier on the surface and the silica-coated quantum dots bound with the third modifier on the surface are mixed to make the silica (O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si ((O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (
  • the step of O-) 3 binding is: under the condition of ultraviolet light or the action of a second initiator, the surface of the graphene nanosheets bound with the fourth modifier and the surface bound with the third modifier dioxide
  • the silicon-coated quantum dots are mixed to cause a free radical reaction between a vinyl group and a mercapto group to obtain the composite material.
  • the thiol group and the vinyl group are combined by Click chemistry. Under the action of a second initiator or ultraviolet light, the thiol group in the modifier generates a free radical reaction with the vinyl group in another modifier, which is formed by the reaction ( O-) 3 Si-R 4 -SCH 2 CH 2 -R 5 -Si (O-) 3 , connecting the silica-coated quantum dots and the graphene nanosheets together to obtain a structure unique to the embodiment of the present application. Composite material.
  • the second initiator is selected from at least one of dimethylphenyl phosphorus and triethylamine.
  • the embodiment of the present application provides an application of a composite material, and the composite material obtained in the embodiment of the present application or the composite material obtained by the preparation method in the embodiment of the present application is used as a light emitting layer material of a quantum dot light emitting diode.
  • the composite materials provided in the embodiments of the present application have good stability and luminous efficiency. Therefore, when the composite materials can be applied to the light emitting layer of a QLED device, the composite material not only improves the luminous efficiency of the quantum dots, but also improves the internal quality of the QLED device. The external quantum efficiency increases the luminous efficiency of QLED devices.
  • a method for preparing a composite material includes the following steps:
  • the silica-coated CdSe / CdS quantum dot particles prepared above were dispersed in an aqueous solution, and then 0.5 ml of ⁇ -aminopropyltriethoxysilane and 2 ml of ammonia were added to the solution, and then placed in The reaction was performed at 50 ° C for 2 hours. After the reaction was completed, the product was washed with water and dried to obtain silica-coated CdSe / CdS quantum dot particles having amino functional groups on the surface;
  • silica-coated CdSe / CdS quantum dot particles having an amino functional group on the surface are dispersed in water, 5 mg of trimellitic anhydride is added to the above reaction system, and the mixture is stirred at room temperature for 8 hours. After completion, the product was washed with water and dried to obtain silica-coated CdSe / CdS quantum dot particles having a carboxyl functional group on the surface.
  • the silica-coated InP / ZnS quantum dot particles prepared above were dispersed in an aqueous solution, and then 0.5 ml of ⁇ -aminopropyltriethoxysilane and 2 ml of ammonia water were added to the above solution, and then placed in The reaction was performed at 50 ° C for 2 hours. After the reaction was completed, the product was washed with water and dried to obtain silica-coated InP / ZnS quantum dot particles having amino functional groups on the surface;
  • silica-coated CdSe / CdS quantum dot particles prepared above were dispersed in an aqueous solution, and then 200 ul of 3-aminopropyltriethoxysilane was added to the solution, and the reaction was performed at room temperature for 12 hours. After the product is washed with water and dried, silica-coated CdSe / CdS quantum dot particles having amino functional groups on the surface are obtained;
  • silica-coated InP / ZnS quantum dot particles prepared above were dispersed in an aqueous solution, and then 200 ul of 3-aminopropyltriethoxysilane was added to the solution, and the reaction was performed at room temperature for 12 hours. After the product is washed and dried with water, silica-coated InP / ZnS quantum dot particles having amino functional groups on the surface are obtained;
  • the silica-coated CdSe / CdS quantum dot particles prepared above were dispersed in an aqueous solution, and then 0.5 ml of mercaptopropyltrimethoxysilane was added to the solution, and the mixture was allowed to react at 80 ° C for 2 hours. After the end, the product is washed with water and dried to obtain silica-coated CdSe / CdS quantum dot particles having a mercapto functional group on the surface;
  • the silica-coated InP / ZnS quantum dot particles prepared above were dispersed in an aqueous solution, and then 0.5 ml of mercaptopropyltrimethoxysilane was added to the solution, and the mixture was allowed to react at 80 ° C for 2 hours. After the end, the product was washed with water and dried to obtain silica-coated InP / ZnS quantum dot particles with thiol functional groups on the surface;
  • the silica-coated CdSe / CdS quantum dot particles prepared above were dispersed in an aqueous solution, and then 0.5 ml of vinyltriethoxysilane was added to the solution, and the mixture was allowed to react at 80 ° C for 2 hours. After the end, the product was washed with water and dried to obtain silica-coated CdSe / CdS quantum dot particles with vinyl functional groups on the surface;
  • the above-prepared silica-coated InP / ZnS quantum dot particles were dispersed in an aqueous solution, and then 0.5 ml of vinyltriethoxysilane was added to the above solution, and the mixture was allowed to react at 80 ° C for 2 hours. After the end, the product was washed with water and dried to obtain silica-coated InP / ZnSS quantum dot particles with vinyl functional groups on the surface;

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Abstract

涉及一种复合材料及其制备方法和应用。所述复合材料包括二氧化硅包覆量子点，以及结合在所述二氧化硅包覆量子点表面的石墨烯纳米片；其中，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，且所述石墨烯纳米片与所述二氧化硅层通过(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3或(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，R 1、R 2、R 4、R 5分别独立选自烃基或烃基衍生物，R 3选自烃基、烃基衍生物、芳基或芳基衍生物。该复合材料能够在不影响量子点的固有光学性能的前提下进一步提高量子点的稳定性，从而提高发光效率。

Description

复合材料及其制备方法和应用
本申请要求于2018年09月30日在中国专利局提交的、申请号为2018111558274、发明名称为“复合材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及纳米材料技术领域，具体涉及一种复合材料及其制备方法和应用。
背景技术
量子点是一种颗粒半径小于或接近于激子波尔半径，通常由II-VI或III-V族元素组成的半导体纳米粒子。量子点受外界光或电致激发后，处于激发态的电子向较低能级跃迁，以光能的形式辐射能量，发出荧光。量子点具有制备简单、半峰宽窄、颗粒小无散射损失、发光效率高和光谱覆盖范围广等优点，在新型显示、照明和生物标记领域具有广泛的应用前景。
量子点在真正实现大规模商业化前，亟需解决的问题是其稳定性问题。一方面，量子点自身具有较小的尺寸分布，大多在10nm以下，比表面积非常大，在制备和使用的过程中非常容易受环境因素的影响。比如：量子点长期暴露在空气中，空气中水、氧的接触会造成量子点表面存在大量的缺陷，从而大大降低其发光效率和使用寿命。另一方面，量子点表面具有大量的长链有机配体，这些有机配体在较高温度下不稳定，非常容易脱落，从而显著影响其QLED器件性能。因此，量子点自身稳定性差的问题极大的限制了量子点的广泛使用。现阶段，最常用的提高量子点稳定性的方法是采用聚合物或二氧化硅进行包覆，但是这些方法普遍存在一些不足，比如会增大量子点尺寸、损害量子点的表面，造成其发光效率降低。
因此，相关技术有待改进和发展。
技术问题
本申请实施例的目的之一在于：提供一种复合材料及其制备方法和应用，旨在解决现有量子点的稳定性差、发光效率低的技术问题。
技术解决方案
为解决上述技术问题，本申请实施例采用的技术方案是：
第一方面，提供了一种复合材料，所述复合材料包括二氧化硅包覆量子点，以及结合在所述二氧化硅包覆量子点表面的石墨烯纳米片；其中，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，且所述石墨烯纳米片与所述二氧化硅层通过(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3或(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，R 1、R 2、R 4、R 5分别独立选自烃基或烃基衍生物，R 3选自烃基、 烃基衍生物、芳基或芳基衍生物。
第二方面，提供了一种复合材料的制备方法，包括以下步骤：
提供二氧化硅包覆量子点，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，所述二氧化硅层的表面结合第一修饰剂，所述第一修饰剂为(O-) 3Si-R 1-NH 2或者(O-) 3Si-R 1-NHCO-R 3-COOH，其中，R 1选自烃基或烃基衍生物，R 3选自烃基、烃基衍生物、芳基或芳基衍生物；
提供石墨烯纳米片，所述石墨烯纳米片表面结合第二修饰剂，所述第二修饰剂为(O-) 3Si-R 2-NHCO-R 3-COOH或(O-) 3Si-R 2-NH 2，其中，R 2选自烃基或烃基衍生物，
将表面结合所述第二修饰剂的石墨烯纳米片与表面结合所述第一修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第一修饰剂与所述第二修饰剂反应形成的(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合，得到复合材料；
其中，当第一修饰剂为(O-) 3Si-R 1-NH 2时，所述第二修饰剂为(O-) 3Si-R 2-NHCO-R 3-COOH；当第一修饰剂为(O-) 3Si-R 1-NHCO-R 3-COOH时，所述第二修饰剂为(O-) 3Si-R 2-NH 2。
以及，另一种复合材料的制备方法，包括以下步骤：
提供二氧化硅包覆量子点，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，所述二氧化硅层的表面结合第三修饰剂，所述第三修饰剂为(O-) 3Si-R 4-SH或(O-) 3Si-R 5-CH 2＝CH 2，其中，R 4、R 5分别独立选自烃基或烃基衍生物；
提供石墨烯纳米片，所述石墨烯纳米片表面结合第四修饰剂，所述第四修饰剂为(O-) 3Si-R 5-CH 2＝CH 2或(O-) 3Si-R 4-SH；
将表面结合所述第四修饰剂的石墨烯纳米片与表面结合所述第三修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第三修饰剂与所述第四修饰剂反应形成的(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，得到复合材料；
其中，当第三修饰剂为(O-) 3Si-R 4-SH时，第四修饰剂为(O-) 3Si-R 5-CH 2＝CH 2；当第三修饰剂为(O-) 3Si-R 5-CH 2＝CH 2时，第四修饰剂为(O-) 3Si-R 4-SH。
第三方面，提供一种复合材料的应用，将本申请的上述复合材料或本申请的上述制备方法得到的复合材料用作量子点发光二极管的发光层材料。
有益效果
本申请实施例提供的复合材料的有益效果在于：一方面，石墨烯纳米片不仅具有优越的阻水/氧能力，可有效阻挡水/氧对量子点对侵蚀，从而避免外界环境对复合材料中的量子点的不可逆影响，而且石墨烯纳米片还具有优异的热传导性能，这样可以提高复合材料的热稳定性；另一方面，如果石墨烯纳米片直接与量子点接触时会造成量子点荧光猝灭的缺陷，而二氧化硅层包覆在量子点表面可以有效地避免石墨 烯纳米片直接与量子点接触，同时二氧化硅层可以进一步提高量子点的稳定性。因此，该特有结构的复合材料充分发挥各组分的优异性能，通过二氧化硅层和石墨烯纳米片的协同作用，能够在不影响量子点的固有光学性能的前提下进一步提高量子点的稳定性，从而提高发光效率。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或示范性技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1是本申请一实施例提供的复合材料的示意图；
图2是本申请一实施例提供的石墨烯纳米片与二氧化硅层通过(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合的复合材料的结构通式示意图；
图3是本申请一实施例提供的石墨烯纳米片与二氧化硅层通过或(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合的复合材料的结构通式示意图；
图4是本申请一实施例提供的复合材料的制备方法流程示意图；
图5是本申请一实施例提供的复合材料的制备方法流程示意图。
具体实施方式
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
需要理解的是，术语“第一”、“第二”、等仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。
本申请一些实施例提供了一种复合材料，所述复合材料包括二氧化硅包覆量子点，以及结合在所述二氧化硅包覆量子点表面的石墨烯纳米片；其中，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，且所述石墨烯纳米片与所述二氧化硅层通过(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3或(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，R 1、R 2、R 4、R 5分别独立选自烃基或烃基衍生物，R 3选自烃基、烃基衍生物、芳基或芳基衍生物。
本申请实施例提供的复合材料由位于内部的量子点、包覆在该量子点表面的二氧化硅层以及结合在二氧化硅层外表面的石墨烯纳米片三部分组成，量子点表面可以直接形成二氧化硅层(即二氧化硅包覆量子点)，但二氧化硅层不能和石墨烯纳米片直接连接，因此通过(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3或(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3将二氧化硅层与石墨烯纳米片有效连接起来，从而形成本申请实施例的复合材料；一方面，石墨烯纳米片不仅具有优越的阻水/氧能力，可有效阻挡水/氧对量子点对侵蚀，从而避免外界环境对复合材料中的量子点的不可逆影响，而且石墨烯纳米片还具有优异的热传导性能，这 样可以提高复合材料的热稳定性；另一方面，如果石墨烯纳米片直接与量子点接触时会造成量子点荧光猝灭的缺陷，而二氧化硅层包覆在量子点表面可以有效地避免石墨烯纳米片直接与量子点接触，同时二氧化硅层可以进一步提高量子点的稳定性。因此，该特有结构的复合材料充分发挥各组分的优异性能，通过二氧化硅层和石墨烯纳米片的协同作用，能够在不影响量子点的固有光学性能的前提下进一步提高量子点的稳定性，从而提高发光效率。
如图1-3所示，其中11为量子点，12为二氧化硅层，13为石墨烯纳米片；形成的两种复合材料的结构通式示意图分别如图2、图3所示。
对于以(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合方式的结构形式，复合材料可以是“石墨烯纳米片(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3二氧化硅包覆量子点”，也可以是“二氧化硅包覆量子点(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3石墨烯纳米片”；因该连接部位的结构对称，所以二氧化硅包覆量子点和石墨烯纳米片的两种连接方式都可以用图2所示的一种通式表示。
对于以(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合方式的结构形式，复合材料可以是“石墨烯纳米片(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3二氧化硅包覆量子点”，也可以是“二氧化硅包覆量子点(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3石墨烯纳米片”；因该连接部位的结构不对称，所以二氧化硅包覆量子点和石墨烯纳米片的两种连接方式分别用图3a和图3b的通式表示。
在一实施例中，本申请实施例提供的复合材料中，量子点包括但不限于II-VI族量子点、III-V族量子点、IV-VI族化合物、IV族化合物、I-III-VI族量子点的至少一种。具体地，包括II-VI族的CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe；CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS；CdZnSeS、CdZnSeTe、CdZnSTe；或III-V族的InP、InAs、GaP、GaAs、GaSb、AlN、AlP；InAsP；InNP、InNSb、GaAlNP、InAlNP、或I-III-VI 2族的CuInS 2、CuInSe 2、AgInS 2中以上任意一种或多种的组合等。量子点可以是单核量子点，也可以是核壳量子点。
在一实施例中，本申请实施例提供的复合材料中，所述二氧化硅层的厚度为2-20nm；如二氧化硅层的厚度太小，则量子点的稳定性不够，如二氧化硅层的厚度太厚，则影响量子点的发光性能；因此，在该厚度范围内，量子点的稳定性和发光性的综合效果最佳。
在一实施例中，本申请实施例提供的复合材料中，所述石墨烯纳米片的尺寸2-20nm。具体地，不同尺寸的石墨烯纳米片和二氧化硅包覆量子点的复合可以有不同的存在方式，它们的相对尺寸不一样其包覆效果不同；当石墨烯的尺寸较大时，如10-20nm，一个石墨烯纳米片中可以连接有多个(如两个以上)二氧化硅包覆量子点；当石墨烯的尺寸较适中时，如5-10nm，一个二氧化硅包覆量子点表面会有2～3片的石墨烯纳米片；当石墨烯的尺寸较小时，如2-5nm，一个二氧化硅包覆量子点表面会有较多(如4片以上)的石墨烯纳米片。
在一实施例中，本申请实施例提供的复合材料中，所述石墨烯纳米片与所述二氧化硅层通过 (O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合，R 1和R 2分别独立选自碳原子数为2-20的烃基或碳原子数为2-20的烃基衍生物，R 3选自碳原子数为2-20的烃基、碳原子数为2-20的烃基衍生物、碳原子数为6-20的芳基或碳原子数为6-20的芳基衍生物。
在一实施例中，R 1和R 2分别独立选自-CH 2CH 2-、-CH 2CH 2CH 2-、-CH 2CH 2CH 2CH 2-、-CH 2CH 2NHCH 2CH 2-、-CH 2CH 2CH 2NHCH 2CH 2-和-CH 2CH 2CH 2NHCH 2CH 2CH 2-中的任意一种；R 3选自-CH 2CH 2-、-CH 2CH 2CH 2-、
Figure PCTCN2019103583-appb-000001
Figure PCTCN2019103583-appb-000002
中的任意一种。
在一实施例中，本申请实施例提供的复合材料中，所述石墨烯纳米片与所述二氧化硅层通过(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，R 4和R 5分别独立选自碳原子数为2-20烃基或碳原子数为2-20烃基衍生物。在一实施例中，R 4和R 5分别独立选自-CH 2CH 2-或-CH 2CH 2CH 2-。
另一方面，本申请实施例提供一种复合材料的制备方法，如图4所示，该制备方法包括以下步骤：
S01：提供二氧化硅包覆量子点，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，所述二氧化硅层的表面结合第一修饰剂，所述第一修饰剂为(O-) 3Si-R 1-NH 2或者(O-) 3Si-R 1-NHCO-R 3-COOH，其中，R 1选自烃基或烃基衍生物，R 3选自烃基、烃基衍生物、芳基或芳基衍生物；
S02：提供石墨烯纳米片，所述石墨烯纳米片表面结合第二修饰剂，所述第二修饰剂为(O-) 3Si-R 2-NHCO-R 3-COOH或(O-) 3Si-R 2-NH 2，其中，R 2选自烃基或烃基衍生物；
S03：将表面结合所述第二修饰剂的石墨烯纳米片与表面结合所述第一修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第一修饰剂与所述第二修饰剂反应形成的(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合，得到复合材料；
其中，当第一修饰剂为(O-) 3Si-R 1-NH 2时，所述第二修饰剂为(O-) 3Si-R 2-NHCO-R 3-COOH；当第一修饰剂为(O-) 3Si-R 1-NHCO-R 3-COOH时，所述第二修饰剂为(O-) 3Si-R 2-NH 2。
本申请实施例的复合材料的制备方法工艺简单、安全、易操作，先在二氧化硅包覆量子点表面和石墨烯纳米片表面各自进行修饰，使各自表面连上可以相互反应的修饰剂，这样通过表面连接的修饰剂 反应形成(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3，将二氧化硅包覆量子点和石墨烯纳米片连在一起，从而得到本申请实施例特有结构的复合材料。
上述制备方法中，当所述第一修饰剂为(O-) 3Si-R 1-NH 2时，所述第一修饰剂选自带氨基的硅烷偶联剂，所述第二修饰剂选自带氨基的硅烷偶联剂与酸酐进行缩合反应得到的修饰剂。即，第一修饰剂选自带氨基的硅烷偶联剂(即氨基硅烷偶联剂)，此时，将二氧化硅包覆量子点进行修饰处理的过程可以包括：直接用带氨基的硅烷偶联剂对二氧化硅包覆量子点进行氨基化改性，得到“二氧化硅包覆量子点(O-) 3Si-R 1-NH 2”。而第二修饰剂选自带氨基的硅烷偶联剂与酸酐进行缩合反应得到的修饰剂，此时，石墨烯纳米片进行修饰处理的过程可以包括：先用带氨基的硅烷偶联剂对石墨烯纳米片进行氨基化改性，然后与酸酐反应，得到“石墨烯纳米片-(O-) 3Si-R 2-NHCO-R 3-COOH”。最后，通过“石墨烯纳米片-(O-) 3Si-R 2-NHCO-R 3-COOH”与“H 2N-R 1-Si(O-) 3-二氧化硅包覆量子点”反应，生成复合材料(图2)。
或者，当所述第二修饰剂为(O-) 3Si-R 2-NH 2时，所述第二修饰剂选自带氨基的硅烷偶联剂，所述第一修饰剂选自带氨基的硅烷偶联剂与酸酐进行缩合反应得到的修饰剂。即，第一修饰剂选自带氨基的硅烷偶联剂(即氨基硅烷偶联剂)与酸酐缩合反应得到的修饰剂，此时，二氧化硅包覆量子点进行修饰处理的过程可以包括：先用带氨基的硅烷偶联剂对氧化硅包覆量子点进行氨基化改性，然后与酸酐反应，得到“二氧化硅包覆量子点(O-) 3Si-R 1-NHCO-R 3-COOH”。而第二修饰剂选自带氨基的硅烷偶联剂，此时，石墨烯纳米片进行修饰处理的过程可以包括：直接用带氨基的硅烷偶联剂对石墨烯纳米片进行氨基化改性，生成“H 2N-R 2-Si(O-) 3-石墨烯纳米片”。最后，“石墨烯纳米片-(O-) 3Si-R 2-NH 2”与“HOOC-R 3-CONH-R 1-Si(O-) 3-二氧化硅包覆量子点”反应，生成复合材料。
上述带氨基的硅烷偶联剂具体选自单氨基硅烷偶联剂、双氨基硅烷偶联剂和三氨基硅烷偶联剂中的至少一种。在一实施例中，氨基硅烷偶联剂为3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、氨乙基氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷。所述酸酐选自苯偏三酸酐、丁二酸酐、四氯苯二甲酸酐、环戊四酸二酐、四氢邻苯二甲酸酐、邻苯二甲酸酐和二苯醚四酸二酐中的至少一种。而R 1、R 2即为带氨基的硅烷偶联剂中的烃基或烃基衍生物，R 3即为酸酐中的烃基、烃基衍生物、芳基或芳基衍生物。在本申请一实施例中，R 1和R 2分别独立选自碳原子数为2-20的烃基或碳原子数为2-20的烃基衍生物，R 3选自碳原子数为2-20的烃基、碳原子数为2-20的烃基衍生物、碳原子数为6-20的芳基或碳原子数为6-20的芳基衍生物。在一实施例中，R 1和R 2分别独立选自-CH 2CH 2-、-CH 2CH 2CH 2-、-CH 2CH 2CH 2CH 2-、-CH 2CH 2NHCH 2CH 2-、-CH 2CH 2CH 2NHCH 2CH 2-和-CH 2CH 2CH 2NHCH 2CH 2CH 2-中的 任意一种；R 3选自-CH 2CH 2-、-CH 2CH 2CH 2-、
Figure PCTCN2019103583-appb-000003
Figure PCTCN2019103583-appb-000004
中的任意一种。
在一实施例中，上述步骤S01和S02中：石墨烯纳米片或二氧化硅包覆量子点的氨基化修饰具体过程为：(1)将石墨烯纳米片或二氧化硅包覆量子点分散在极性溶剂中，形成石墨烯纳米片或二氧化硅包覆量子点溶液；(2)室温下，向上述石墨烯纳米片或二氧化硅包覆量子点复合溶液中加入带氨基的硅烷偶联剂和催化剂，并在40～150℃下反应20min～24h，待反应结束后，通过水清洗、干燥后，即可得到表面氨基化改性的石墨烯纳米片或二氧化硅包覆量子点。
在一实施例中，上述极性溶剂包括水、乙醇、甲醇、甘油、丙二醇、乙腈、丙醇、二氧六环、四氢呋喃、甲乙酮、正丁醇等中的至少一种；催化剂包括氨气、氨水、二甲胺、二乙胺、三甲胺、三乙胺、吡啶、四甲基氢氧化铵、四乙基氢氧化铵、四叔丁基氢氧化铵等中的至少一种；催化剂在混合溶液中的体积浓度为0.1～100ml/L；带氨基的硅烷偶联剂在混合溶液中的体积浓度为0.1～50ml/ml。
在一实施例中，上述步骤S01和S02中：石墨烯纳米片或二氧化硅包覆量子点的羧基化修饰的具体过程包括：(1)将上述表面氨基化改性的石墨烯纳米片或二氧化硅包覆量子点分散在极性溶剂中，形成表面氨基化改性的石墨烯纳米片或二氧化硅包覆量子点溶液；(2)室温下，向上述表面氨基化改性的石墨烯纳米片或二氧化硅包覆量子点容易中加入酸酐，并在室温下反应20min～24h，待反应结束后，通过水清洗、干燥后，即可得到表面羧基化改性的石墨烯纳米片或二氧化硅包覆量子点。
在一实施例中，上述极性溶剂包括水、乙醇、甲醇、甘油、丙二醇、乙腈、丙醇、二氧六环、四氢呋喃、甲乙酮、正丁醇等。酸酐与表面氨基化改性的石墨烯纳米片或二氧化硅包覆量子点的质量比为0.01～10:1。
在一实施例中，所述二氧化硅包覆量子点的制备方法包括如下：将全氢聚硅氮烷溶液和量子点溶液进行混合处理，使量子点表面形成二氧化硅层。
传统二氧化硅包覆量子点的制备过程需使用水或氨或其他催化剂试剂，由于量子点具有很大的比表面积，这些添加的水、氨或催化剂会在一定程度上降低量子点的荧光产率。而本申请实施例的二氧化硅包覆量子点的制备，利于全氢聚硅氮烷在低温下快速水解、氧化，从而在量子点表面形成致密地二氧 化硅层，该方法可以有效的避免常规包覆过程中须使用氨或催化剂等会对量子点造成不可逆的影响。
具体地，本实施例的二氧化硅包覆量子点的制备包括：(1)将量子点分散在非极性溶剂中，形成量子点溶液；(2)将全氢聚硅氮烷分散在极性溶剂中，形成倍全氢聚硅氮烷溶液；(2)室温下，向上述步骤(1)所述的量子点溶液中，加入全氢聚硅氮烷溶液，并于室温下进行反应20～24h，即可得到二氧化硅包裹的量子点；
在一实施例中，全氢聚硅氮烷与量子点的质量比为0.01～10:1，量子点在非极性溶剂中的浓度为0.01～300mg/ml。溶剂与非极性溶剂的体积比为0.1～100:1。上述极性溶剂包括己烷、环己烷、甲苯、氯苯、乙醚、丁醚、四氢呋喃、1，4-二氧六环、丙酮、环己酮、甲基异丁基酮、乙二醇二乙醚、二乙二醇二乙醚、二乙二醇乙醚、乙二醇二乙醚、乙二醇乙醚；
在一实施例中，在步骤S03中：将表面结合所述第二修饰剂的石墨烯纳米片与表面结合所述第一修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第一修饰剂与所述第二修饰剂反应形成的(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合的步骤包括：：在酸性条件和第一引发剂作用的条件下，将所述表面结合所述第二修饰剂的石墨烯纳米片和表面结合所述第一修饰剂的二氧化硅包覆量子点混合，进行缩合反应，得到所述复合材料。
所述第一引发剂选自碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS)中的至少一种；在酰胺缩合反应中，EDC或NHS用作羧基的活化试剂，通过EDC或NHS可以提高带氨基与羧基的偶联效率，当EDC和NHS的摩尔量比为1:1使用使，酰胺缩合反应效率最高。更进一步地，所述酸性条件的pH为4～7。
具体地，室温下，将表面结合所述第一修饰剂的二氧化硅包覆量子点溶液的pH调整至4～7，然后加入表面结合所述第二修饰剂的石墨烯纳米片溶液。在EDC/NHS的偶联作用下，进行酰胺键的复合。或，将表面结合所述第二修饰剂的石墨烯纳米片溶液的pH调整至4～7，然后加入表面结合所述第一修饰剂的二氧化硅包覆量子点溶液。在EDC/NHS的偶联作用下，进行酰胺键的复合，即可制备完成复合材料的制备。
本申请实施例还提供一种复合材料的制备方法，如图5所示，该制备方法包括以下步骤：
T01：提供二氧化硅包覆量子点，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，所述二氧化硅层的表面结合第三修饰剂，所述第三修饰剂为(O-) 3Si-R 4-SH或(O-) 3Si-R 5-CH 2＝CH 2，其中，R 4、R 5分别独立选自烃基或烃基衍生物；
T02：提供石墨烯纳米片，所述石墨烯纳米片表面结合第四修饰剂，所述第四修饰剂为(O-) 3Si-R 5-CH 2＝CH 2或(O-) 3Si-R 4-SH；
T03：将表面结合所述第四修饰剂的石墨烯纳米片与表面结合所述第三修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第三修饰剂与所述第四修饰剂 反应形成的(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，得到复合材料；
其中，当第三修饰剂为(O-) 3Si-R 4-SH时，第四修饰剂为(O-) 3Si-R 5-CH 2＝CH 2；当第三修饰剂为(O-) 3Si-R 5-CH 2＝CH 2时，第四修饰剂为(O-) 3Si-R 4-SH。
本申请实施例的复合材料的制备方法工艺简单、安全、易操作，先在二氧化硅包覆量子点表面和石墨烯纳米片表面各自进行修饰，使各自表面连上可以相互反应的修饰剂，这样通过表面连接的修饰剂反应形成(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3，将二氧化硅包覆量子点和石墨烯纳米片连在一起，从而得到本申请实施例特有结构的复合材料。
上述制备方法中，当所述第三修饰剂为(O-) 3Si-R 4-SH时，所述第三修饰剂选自带巯基的硅烷偶联剂，所述第四修饰剂选自带乙烯基的硅烷偶联剂。即，第三修饰剂选自带巯基的硅烷偶联剂(即巯基硅烷偶联剂)，此时，将二氧化硅包覆量子点进行修饰处理的过程可以包括：直接用带巯基的硅烷偶联剂对二氧化硅包覆量子点进行巯基化改性，得到“二氧化硅包覆量子点(O-) 3Si-R 4-SH”。而第四修饰剂选自带乙烯基的硅烷偶联剂，此时，石墨烯纳米片进行修饰处理的过程可以包括：直接用带乙烯基的硅烷偶联剂对石墨烯纳米片进行乙烯基化改性，得到“石墨烯纳米片-(O-) 3Si-R 5-CH 2＝CH”。最后，通过“石墨烯纳米片-(O-) 3Si-R 5-CH 2＝CH”与“二氧化硅包覆量子点(O-) 3Si-R 4-SH”反应，生成复合材料(图3b)。
或者，当所述第四修饰剂为(O-) 3Si-R 4-SH，所述第四修饰剂选自带巯基的硅烷偶联剂，所述第三修饰剂选自带乙烯基的硅烷偶联剂。即，第三修饰剂选自带乙烯基的硅烷偶联剂(即乙烯基硅烷偶联剂)，此时，二氧化硅包覆量子点进行修饰处理的过程可以包括：直接用带乙烯基的硅烷偶联剂对氧化硅包覆量子点进行乙烯基化改性，得到“二氧化硅包覆量子点-(O-) 3Si-R 5-CH 2＝CH”。而第四修饰剂选自带巯基的硅烷偶联剂，此时，石墨烯纳米片进行修饰处理的过程可以包括：直接用带巯基的硅烷偶联剂对石墨烯纳米片进行巯基化改性，生成“石墨烯纳米(O-) 3Si-R 4-SH”。最后，“石墨烯纳米(O-) 3Si-R 4-SH”与“二氧化硅包覆量子点-(O-) 3Si-R 5-CH 2＝CH”反应，生成复合材料(图3a)。
上述带巯基的硅烷偶联剂选自γ-巯基丙基三甲氧基硅烷和γ-巯基丙基三乙氧基硅烷中的至少一种；带乙烯基的硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三氯硅烷、乙烯基三(β-甲氧基乙氧基)硅烷、乙烯基三叔丁氧基硅烷、乙烯基三叔丁基过氧硅烷和乙烯基三乙酰氧基硅烷中的至少一种。而R 4即为带巯基的硅烷偶联剂中的烃基或烃基衍生物，具体可以是碳原子数为2-20的烃基或烃基衍生物；R 5即为带乙烯基的硅烷偶联剂中的烃基或烃基衍生物，具体可以是碳原子数为2-20的烃基或烃基衍生物。本申请一实施例中，R 4和R 5分别独立选自-CH 2CH 2-或-CH 2CH 2CH 2-。
在一实施例中，在上述步骤T01和T02中：石墨烯纳米片或二氧化硅包覆量子点的巯基化修饰具体过程为：(1)将石墨烯纳米片或二氧化硅包覆量子点分散在极性溶剂中，形成石墨烯纳米片或二氧化硅包覆量子点溶液；(2)室温下，向上述石墨烯纳米片或二氧化硅包覆量子点溶液中加入带巯基的硅烷偶联剂，并在40～150℃下反应20min～24h，待反应结束后，通过水清洗、干燥后，即可得到表面巯 基化改性的石墨烯纳米片或二氧化硅包覆量子点。
上述极性溶剂包括水、乙醇、甲醇、甘油、丙二醇、乙腈、丙醇、二氧六环、四氢呋喃、甲乙酮、正丁醇等中的至少一种；带巯基的硅烷偶联剂在混合溶液中的体积浓度为0.1～50ml/ml。
在一实施例中，在上述步骤T01和T02中：石墨烯纳米片或二氧化硅包覆量子点的乙烯基化修饰具体过程为：(1)将石墨烯纳米片或二氧化硅包覆量子点分散在极性溶剂中，形成石墨烯纳米片或二氧化硅包覆量子点溶液；(2)室温下，向上述石墨烯纳米片或二氧化硅包覆量子点溶液中加入带乙烯基的硅烷偶联剂，并在40～150℃下反应20min～24h，待反应结束后，通过水清洗、干燥后，可得到表面巯基化改性的石墨烯纳米片或二氧化硅包覆量子点。
上述极性溶剂包括水、乙醇、甲醇、甘油、丙二醇、乙腈、丙醇、二氧六环、四氢呋喃、甲乙酮、正丁醇等。
在一实施例中，上述步骤T03中：将表面结合所述第四修饰剂的石墨烯纳米片与表面结合所述第三修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第三修饰剂与所述第四修饰剂反应形成的(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合的步骤为：在紫外光照或第二引发剂作用的条件下,将所述表面结合所述第四修饰剂的石墨烯纳米片和表面结合所述第三修饰剂的二氧化硅包覆量子点混合,使乙烯基与巯基发生自由基反应，反应得到所述复合材料。
巯基与乙烯基通过Click化学作用结合，在第二引发剂作用或紫外光照条件下，修饰剂中的巯基产生自由基与另一种修饰剂中的乙烯基发生自由基反应，这样通过反应形成(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3，将二氧化硅包覆量子点和石墨烯纳米片连在一起，从而得到本申请实施例特有结构的复合材料。
在一实施例中，第二引发剂选自二甲基苯基磷和三乙基胺中的至少一种。
最后，本申请实施例提供一种复合材料的应用，将本申请实施例的上述复合材料或本申请实施例的上述制备方法得到的复合材料用作量子点发光二极管的发光层材料。
本申请实施例提供的复合材料具有很好的稳定性和发光效率，因此复合材料可以应用于QLED器件的发光层时，该复合材料不仅提高量子点的发光效率，同时，提高了QLED器件的内、外量子效率，增加了QLED器件的发光效率。
本申请先后进行过多次试验，现举一部分试验结果作为参考对申请进行进一步详细描述，下面结合具体实施例进行详细说明。
实施例1
一种复合材料的制备方法，包括如下步骤：
1.二氧化硅包覆CdSe/CdS量子点颗粒
室温下，取30ml，10mg/ml的CdSe/CdS的正己烷溶液，将其放入到一个250ml的圆底烧瓶中， 向其中加入50mg全氢聚硅氮烷的甲基异丁基酮溶液3ml，室温下充分搅拌2h，得到二氧化硅包覆CdSe/CdS量子点颗粒。
2.表面具有羧基官能团的二氧化硅包覆CdSe/CdS量子点颗粒
(1)室温下，将上述制备的二氧化硅包覆CdSe/CdS量子点颗粒分散在水溶液中，然后向上述溶液中加入0.5mlγ-氨丙基三乙氧基硅烷和2ml氨水，再置于50℃下反应2h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有氨基官能团的二氧化硅包覆CdSe/CdS量子点颗粒；
(2)将300mg干燥后的表面具有氨基官能团的二氧化硅包覆CdSe/CdS量子点颗粒分散水中，向上述反应体系中加入5mg的苯偏三酸酐，再置于室温下搅拌8h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有羧基官能团的二氧化硅包覆CdSe/CdS量子点颗粒。
3.表面进行氨基化的石墨烯的制备
取20ml，10mg/ml的石墨烯纳米颗粒水溶液，将其放入到一个50ml的圆底烧瓶，剧烈搅拌，向其中加入200ul的3-氨丙基三乙氧基硅烷，室温下反应12h，待反应结束后，通过水清洗、干燥后，得到表面带有氨基官能团的石墨烯纳米颗粒。
4.CdSe/CdS量子点复合颗粒的制备
取上述10ml，10mg/ml的表面具有羧基官能团的二氧化硅包覆CdSe/CdS量子点颗粒的水溶液放入到一个50ml圆底烧瓶中。在剧烈搅拌下，向溶液中加入氨水溶液，直至溶液的pH值为7，然后向溶液中加入磷酸缓存液来稳定溶液的pH。接着继续向溶液中加入1ml，10mg/ml表面带有氨基化的石墨烯颗粒和0.0001mg的EDC的水溶液，在室温下继续反应60mins，得到CdSe/CdS量子点复合颗粒。
实施例2
1.二氧化硅包覆InP/ZnS量子点颗粒
室温下，取30ml，10mg/ml的InP/ZnS的正己烷溶液，将其放入到一个250ml的圆底烧瓶中，向其中加入50mg全氢聚硅氮烷的甲基异丁基酮溶液3ml，室温下充分搅拌2h，得到二氧化硅包覆InP/ZnS量子点颗粒。
2.表面具有羧基官能团的二氧化硅包覆InP/ZnS量子点颗粒
(1)室温下，将上述制备的二氧化硅包覆InP/ZnS量子点颗粒分散在水溶液中，然后向上述溶液中加入0.5mlγ-氨丙基三乙氧基硅烷和2ml氨水，再置于50℃下反应2h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有氨基官能团的二氧化硅包覆InP/ZnS量子点颗粒；
(2)将300mg干燥后的表面具有羧基官能团的二氧化硅包覆InP/ZnS量子点颗粒分散水中，向上述反应体系中加入5mg的苯偏三酸酐，再置于室温下搅拌8h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有羧基官能团的二氧化硅包覆InP/ZnS量子点颗粒。
3.表面进行氨基化的石墨烯的制备
取20ml，10mg/ml的石墨烯纳米颗粒水溶液，将其放入到一个50ml的圆底烧瓶，剧烈搅拌，向其中加入200ul的3-氨丙基三乙氧基硅烷，室温下反应12h，待反应结束后，通过水清洗、干燥后，得到表面带有氨基官能团的石墨烯纳米颗粒。
4.InP/ZnS量子点复合颗粒的制备
取上述10ml，10mg/ml的表面具有羧基官能团的二氧化硅包覆InP/ZnS量子点颗粒的水溶液放入到一个50ml圆底烧瓶中。在剧烈搅拌下，向溶液中加入氨水溶液，直至溶液的pH值为7，然后向溶液中加入磷酸缓存液来稳定溶液的pH。接着继续向溶液中加入1ml，10mg/ml表面带有氨基官能团的石墨烯纳米颗粒和0.0001mg的EDC的水溶液，在室温下继续反应60mins，得到InP/ZnS量子点复合颗粒。
实施例3
1.二氧化硅包覆CdSe/CdS量子点颗粒
室温下，取30ml，10mg/ml的CdSe/CdS的正己烷溶液，将其放入到一个250ml的圆底烧瓶中，向其中加入50mg全氢聚硅氮烷的甲基异丁基酮溶液3ml，室温下充分搅拌2h，得到二氧化硅包覆CdSe/CdS量子点颗粒。
2.表面具有氨基官能团的二氧化硅包覆CdSe/CdS量子点颗粒
室温下，将上述制备的二氧化硅包覆CdSe/CdS量子点颗粒分散在水溶液中，然后向上述溶液中加入200ul的3-氨丙基三乙氧基硅烷，室温下反应12h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有氨基官能团的二氧化硅包覆CdSe/CdS量子点颗粒；
3.表面进行羧基化的石墨烯的制备
(1)取20ml，20mg/ml的石墨烯纳米颗粒水溶液，然后向上述溶液中加入0.5mlγ-氨丙基三乙氧基硅烷和2ml氨水，再置于50℃下反应2h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有氨基官能团的石墨烯纳米颗粒；
(2)将300mg干燥后的表面具有氨基官能团的石墨烯纳米颗粒分散水中，向上述反应体系中加入5mg的苯偏三酸酐，再置于室温下搅拌8h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有羧基官能团的石墨烯纳米颗粒。
4.CdSe/CdS量子点复合颗粒的制备
取上述10ml，10mg/ml的表面具有羧基官能团的石墨烯纳米颗粒的水溶液放入到一个50ml圆底烧瓶中。在剧烈搅拌下，向溶液中加入氨水溶液，直至溶液的pH值为7，然后向溶液中加入磷酸缓存液来稳定溶液的pH。接着继续向溶液中加入1ml，10mg/ml表面带有氨基官能团的二氧化硅包覆的CdSe/CdS量子点颗粒和0.0001mg的EDC的水溶液，在室温下继续反应60mins，得到CdSe/CdS量子点复合颗粒。
实施例4
1.二氧化硅包覆InP/ZnS量子点颗粒
室温下，取30ml，10mg/ml的InP/ZnS的正己烷溶液，将其放入到一个250ml的圆底烧瓶中，向其中加入50mg全氢聚硅氮烷的甲基异丁基酮溶液3ml，室温下充分搅拌2h，得到二氧化硅包覆InP/ZnS量子点颗粒。
2.表面具有氨基官能团的二氧化硅包覆InP/ZnS量子点颗粒
室温下，将上述制备的二氧化硅包覆InP/ZnS量子点颗粒分散在水溶液中，然后向上述溶液中加入200ul的3-氨丙基三乙氧基硅烷，室温下反应12h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有氨基官能团的二氧化硅包覆InP/ZnS量子点颗粒；
3.表面进行羧基化的石墨烯的制备
(1)取20ml，20mg/ml的石墨烯纳米颗粒水溶液，然后向上述溶液中加入0.5mlγ-氨丙基三乙氧基硅烷和2ml氨水，再置于50℃下反应2h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有氨基官能团的石墨烯纳米颗粒；
(2)将300mg干燥后的表面具有氨基官能团的石墨烯纳米颗粒分散水中，向上述反应体系中加入5mg的苯偏三酸酐，再置于室温下搅拌8h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有羧基官能团的石墨烯纳米颗粒。
4.InP/ZnS量子点复合颗粒的制备
取上述10ml，10mg/ml的表面具有羧基官能团的石墨烯纳米颗粒的水溶液放入到一个50ml圆底烧瓶中。在剧烈搅拌下，向溶液中加入氨水溶液，直至溶液的pH值为7，然后向溶液中加入磷酸缓存液来稳定溶液的pH。接着继续向溶液中加入1ml，10mg/ml表面带有氨基官能团的二氧化硅包覆的InP/ZnS量子点颗粒和0.0001mg的EDC的水溶液，在室温下继续反应60mins，得到InP/ZnS量子点复合颗粒。
实施例5
1.二氧化硅包覆CdSe/CdS量子点颗粒
室温下，取30ml，10mg/ml的CdSe/CdS的正己烷溶液，将其放入到一个250ml的圆底烧瓶中，向其中加入50mg全氢聚硅氮烷的甲基异丁基酮溶液3ml，室温下充分搅拌2h，得到二氧化硅包覆CdSe/CdS量子点颗粒。
2.表面具有巯基官能团的二氧化硅包覆CdSe/CdS量子点颗粒
室温下，将上述制备的二氧化硅包覆CdSe/CdS量子点颗粒分散在水溶液中，然后向上述溶液中加入0.5ml巯基丙基三甲氧基硅烷，再置于80℃下反应2h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有巯基官能团的二氧化硅包覆CdSe/CdS量子点颗粒；
3.表面进行乙烯基化的石墨烯的制备
取20ml，10mg/ml的石墨烯纳米颗粒水溶液，将其放入到一个50ml的圆底烧瓶，剧烈搅拌，向其中加入200ul的乙烯基三乙氧基硅烷，室温下反应12h，待反应结束后，通过水清洗、干燥后，得到表面带有乙烯基官能团的石墨烯纳米颗粒。
4.CdSe/CdS量子点复合颗粒的制备
取上述10ml，10mg/ml的表面具有巯基官能团的二氧化硅包覆CdSe/CdS量子点颗粒的水溶液放入到一个50ml圆底烧瓶中。在剧烈搅拌下，加入1ml，10mg/ml表面带有乙烯基官能团的二氧化硅包覆的CdSe/CdS量子点颗粒，在紫外光照和室温下继续反应60mins，得到CdSe/CdS量子点复合颗粒。
实施例6
1.二氧化硅包覆InP/ZnS量子点颗粒
室温下，取30ml，10mg/ml的InP/ZnS的正己烷溶液，将其放入到一个250ml的圆底烧瓶中，向其中加入50mg全氢聚硅氮烷的甲基异丁基酮溶液3ml，室温下充分搅拌2h，得到二氧化硅包覆InP/ZnS量子点颗粒。
2.表面具有巯基官能团的二氧化硅包覆InP/ZnS量子点颗粒
室温下，将上述制备的二氧化硅包覆InP/ZnS量子点颗粒分散在水溶液中，然后向上述溶液中加入0.5ml巯基丙基三甲氧基硅烷，再置于80℃下反应2h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有巯基官能团的二氧化硅包覆InP/ZnS量子点颗粒；
3.表面进行乙烯基化的石墨烯的制备
取20ml，10mg/ml的石墨烯纳米颗粒水溶液，将其放入到一个50ml的圆底烧瓶，剧烈搅拌，向其中加入200ul的乙烯基三乙氧基硅烷，室温下反应12h，待反应结束后，通过水清洗、干燥后，得到表面带有乙烯基官能团的石墨烯纳米颗粒。
4.InP/ZnS量子点复合颗粒的制备
取上述10ml，10mg/ml的表面具有巯基官能团的二氧化硅包覆InP/ZnS量子点颗粒的水溶液放入到一个50ml圆底烧瓶中。在剧烈搅拌下，向溶液中加入1ml，10mg/ml表面带有乙烯基官能团的二氧化硅包覆的InP/ZnS量子点颗粒，在紫外光照和室温下继续反应60mins，得到InP/ZnS量子点复合颗粒。
实施例7
1.二氧化硅包覆CdSe/CdS量子点颗粒
室温下，取30ml，10mg/ml的CdSe/CdS的正己烷溶液，将其放入到一个250ml的圆底烧瓶中，向其中加入50mg全氢聚硅氮烷的甲基异丁基酮溶液3ml，室温下充分搅拌2h，得到二氧化硅包覆CdSe/CdS量子点颗粒。
2.表面具有乙烯基官能团的二氧化硅包覆CdSe/CdS量子点颗粒
室温下，将上述制备的二氧化硅包覆CdSe/CdS量子点颗粒分散在水溶液中，然后向上述溶液中加入0.5ml乙烯基三乙氧基硅烷，再置于80℃下反应2h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有乙烯基官能团的二氧化硅包覆CdSe/CdS量子点颗粒；
3.表面进行巯基化的石墨烯的制备
取20ml，10mg/ml的石墨烯纳米颗粒水溶液，将其放入到一个50ml的圆底烧瓶，剧烈搅拌，向其中加入200ul的巯基丙基三甲氧基硅烷，室温下反应12h，待反应结束后，通过水清洗、干燥后，得到表面带有巯基官能团的石墨烯纳米颗粒。
4.CdSe/CdS量子点复合颗粒的制备
取上述10ml，10mg/ml的表面具有乙烯基官能团的二氧化硅包覆CdSe/CdS量子点颗粒的水溶液放入到一个50ml圆底烧瓶中。在剧烈搅拌下，向溶液中加入1ml，10mg/ml表面带有巯基官能团的二氧化硅包覆的CdSe/CdS量子点颗粒，在紫外光照和室温下继续反应60mins，得到CdSe/CdS量子点复合颗粒。
实施例8
1.二氧化硅包覆InP/ZnS量子点颗粒
室温下，取30ml，10mg/ml的InP/ZnS的正己烷溶液，将其放入到一个250ml的圆底烧瓶中，向其中加入50mg全氢聚硅氮烷的甲基异丁基酮溶液3ml，室温下充分搅拌2h，得到二氧化硅包覆InP/ZnS量子点颗粒。
2.表面具有乙烯基官能团的二氧化硅包覆InP/ZnS量子点颗粒
室温下，将上述制备的二氧化硅包覆InP/ZnS量子点颗粒分散在水溶液中，然后向上述溶液中加入0.5ml乙烯基三乙氧基硅烷，再置于80℃下反应2h，待反应结束后，产物通过水进行清洗、干燥后，得到表面具有乙烯基官能团的二氧化硅包覆InP/ZnSS量子点颗粒；
3.表面进行巯基化的石墨烯的制备
取20ml，10mg/ml的石墨烯纳米颗粒水溶液，将其放入到一个50ml的圆底烧瓶，剧烈搅拌，向其中加入200ul的巯基丙基三甲氧基硅烷，室温下反应12h，待反应结束后，通过水清洗、干燥后，得到表面带有巯基官能团的石墨烯纳米颗粒。
4.InP/ZnS量子点复合颗粒的制备
取上述10ml，10mg/ml的表面具有乙烯基官能团的二氧化硅包覆InP/ZnS量子点颗粒的水溶液放入到一个50ml圆底烧瓶中。在剧烈搅拌下，向溶液中加入1ml，10mg/ml表面带有巯基官能团的二氧化硅包覆的InP/ZnS量子点颗粒，在紫外光照和室温下继续反应60mins，得到InP/ZnS量子点复合颗粒。
以上仅为本申请的可选实施例而已，并不用于限制本申请。对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包 含在本申请的权利要求范围之内。

Claims (20)

  1. 一种复合材料，其特征在于，所述复合材料包括二氧化硅包覆量子点，以及结合在所述二氧化硅包覆量子点表面的石墨烯纳米片；其中，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，且所述石墨烯纳米片与所述二氧化硅层通过(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3或(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，R 1、R 2、R 4、R 5分别独立选自烃基或烃基衍生物，R 3选自烃基、烃基衍生物、芳基或芳基衍生物。
  2. 如权利要求1所述的复合材料，其特征在于，所述二氧化硅层的厚度为2-20nm。
  3. 如权利要求1所述的复合材料，其特征在于，所述石墨烯纳米片的尺寸为2-20nm。
  4. 如权利要求1所述的复合材料，其特征在于，所述石墨烯纳米片与所述二氧化硅层通过(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合，R 1和R 2分别独立选自碳原子数为2-20的烃基或碳原子数为2-20的烃基衍生物，R 3选自碳原子数为2-20的烃基、碳原子数为2-20的烃基衍生物、碳原子数为6-20的芳基或碳原子数为6-20的芳基衍生物。
  5. 如权利要求4所述的复合材料，其特征在于，R 1和R 2分别独立选自-CH 2CH 2-、-CH 2CH 2CH 2-、-CH 2CH 2CH 2CH 2-、-CH 2CH 2NHCH 2CH 2-、-CH 2CH 2CH 2NHCH 2CH 2-和-CH 2CH 2CH 2NHCH 2CH 2CH 2-中的任意一种。
  6. 如权利要求4所述的复合材料，其特征在于，R 3选自-CH 2CH 2-、-CH 2CH 2CH 2-、
    Figure PCTCN2019103583-appb-100001
    中的任意一种。
  7. 如权利要求1所述的复合材料，其特征在于，所述石墨烯纳米片与所述二氧化硅层通过(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，R 4和R 5分别独立选自碳原子数为2-20烃基或碳原子数为2-20烃基衍生物。
  8. 如权利要求7所述的复合材料，其特征在于，R 4和R 5分别独立选自-CH 2CH 2-或-CH 2CH 2CH 2-。
  9. 一种复合材料的制备方法，其特征在于，包括以下步骤：
    提供二氧化硅包覆量子点，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，所述二氧化硅层的表面结合第一修饰剂，所述第一修饰剂为(O-) 3Si-R 1-NH 2或者(O-) 3Si-R 1-NHCO-R 3-COOH，其中，R 1选自烃基或烃基衍生物，R 3选自烃基、烃基衍生物、芳基或芳基 衍生物；
    提供石墨烯纳米片，所述石墨烯纳米片表面结合第二修饰剂，所述第二修饰剂为(O-) 3Si-R 2-NHCO-R 3-COOH或(O-) 3Si-R 2-NH 2，其中，R 2选自烃基或烃基衍生物；
    将表面结合所述第二修饰剂的石墨烯纳米片与表面结合所述第一修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第一修饰剂与所述第二修饰剂反应形成的(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合，得到复合材料；
    其中，当第一修饰剂为(O-) 3Si-R 1-NH 2时，所述第二修饰剂为(O-) 3Si-R 2-NHCO-R 3-COOH；当第一修饰剂为(O-) 3Si-R 1-NHCO-R 3-COOH时，所述第二修饰剂为(O-) 3Si-R 2-NH 2。
  10. 如权利要求9所述的制备方法，其特征在于，将表面结合所述第二修饰剂的石墨烯纳米片与表面结合所述第一修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第一修饰剂与所述第二修饰剂反应形成的(O-) 3Si-R 1-NHCO-R 3-CONH-R 2-Si(O-) 3结合的步骤包括：
    在酸性条件和第一引发剂作用的条件下，将所述表面结合所述第二修饰剂的石墨烯纳米片和表面结合所述第一修饰剂的二氧化硅包覆量子点混合，进行缩合反应，得到所述复合材料。
  11. 如权利要求10所述的制备方法，其特征在于，所述第一引发剂选自碳二亚胺和N-羟基琥珀酰亚胺中的至少一种。
  12. 如权利要求10所述的制备方法，其特征在于，所述酸性条件的pH为4～7。
  13. 如权利要求9所述的制备方法，其特征在于，R 1和R 2分别独立选自碳原子数为2-20的烃基或碳原子数为2-20的烃基衍生物，R 3选自碳原子数为2-20的烃基、碳原子数为2-20的烃基衍生物、碳原子数为6-20的芳基或碳原子数为6-20的芳基衍生物。
  14. 如权利要求13所述的制备方法，其特征在于，R 1和R 2分别独立选自-CH 2CH 2-、-CH 2CH 2CH 2-、-CH 2CH 2CH 2CH 2-、-CH 2CH 2NHCH 2CH 2-、-CH 2CH 2CH 2NHCH 2CH 2-和-CH 2CH 2CH 2NHCH 2CH 2CH 2-中的任意一种；和/或，
    R 3选自-CH 2CH 2-、-CH 2CH 2CH 2-、
    Figure PCTCN2019103583-appb-100002
    Figure PCTCN2019103583-appb-100003
    中的任意一种。
  15. 一种复合材料的制备方法，其特征在于，包括以下步骤：
    提供二氧化硅包覆量子点，所述二氧化硅包覆量子点包括量子点以及包覆在所述量子点表面的二氧化硅层，所述二氧化硅层的表面结合第三修饰剂，所述第三修饰剂为(O-) 3Si-R 4-SH或(O-) 3Si-R 5-CH 2＝CH 2，其中，R 4、R 5分别独立选自烃基或烃基衍生物；
    提供石墨烯纳米片，所述石墨烯纳米片表面结合第四修饰剂，所述第四修饰剂为(O-) 3Si-R 5-CH 2＝CH 2或(O-) 3Si-R 4-SH；
    将表面结合所述第四修饰剂的石墨烯纳米片与表面结合所述第三修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第三修饰剂与所述第四修饰剂反应形成的(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合，得到复合材料；
    其中，当第三修饰剂为(O-) 3Si-R 4-SH时，第四修饰剂为(O-) 3Si-R 5-CH 2＝CH 2；当第三修饰剂为(O-) 3Si-R 5-CH 2＝CH 2时，第四修饰剂为(O-) 3Si-R 4-SH。
  16. 如权利要求15所述的制备方法，其特征在于，将表面结合所述第四修饰剂的石墨烯纳米片与表面结合所述第三修饰剂的二氧化硅包覆量子点混合，使所述二氧化硅包覆量子点与所述石墨烯纳米片之间通过所述第三修饰剂与所述第四修饰剂反应形成的(O-) 3Si-R 4-SCH 2CH 2-R 5-Si(O-) 3结合的步骤为：
    在紫外光照或第二引发剂作用的条件下,将所述表面结合所述第四修饰剂的石墨烯纳米片和表面结合所述第三修饰剂的二氧化硅包覆量子点混合,使乙烯基与巯基发生自由基反应，反应得到所述复合材料。
  17. 如权利要求16所述的制备方法，其特征在于，所述第二引发剂选自二甲基苯基磷和三乙基胺中的至少一种。
  18. 如权利要求15所述的制备方法，其特征在于，R 4和R 5分别独立选自碳原子数为2-20烃基或碳原子数为2-20烃基衍生物。
  19. 如权利要求18所述的制备方法，其特征在于，R 4和R 5分别独立选自-CH 2CH 2-或-CH 2CH 2CH 2-。
  20. 一种复合材料的应用，其特征在于，将权利要求1所述的复合材料用作量子点发光二极管的发光层材料。
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