阅读说明：本技术 蓝色荧光碳量子点修饰的超疏水材料及其制备方法和应用 (Blue fluorescent carbon quantum dot modified super-hydrophobic material and preparation method and application thereof ) 是由 周宁琳 张盼 石绍泽 楚晓红 刘奕含 宋秋娴 高雨萌 冯文立 刘琴 于 2021-07-07 设计创作，主要内容包括：本发明公开了一种蓝色荧光碳量子点修饰的超疏水材料及其制备方法和应用,属于疏水材料技术领域。所述超疏水材料一方面利用改性剂将层状硅铝酸盐进行改性,以便于共水解时SiO-(2)纳米球以及碳量子点能够均匀的分布于该片层的表面；另一方面氟烃基硅烷提供低表面能物质F,使得该材料具备超疏水的两个条件：粗糙结构和低表面能物质。本发明的超疏水材料兼备良好且稳定的转光以及超疏水性能,其作为功能填料能够更好的应用于聚合物自清洁、防尘、转光等领域。(The invention discloses a blue fluorescent carbon quantum dot modified super-hydrophobic material, and a preparation method and application thereof, and belongs to the technical field of hydrophobic materials. On one hand, the super-hydrophobic material utilizes a modifier to modify layered aluminosilicate so as to facilitate SiO during cohydrolysis 2 The nanospheres and the carbon quantum dots can be uniformly distributed on the surface of the sheet layer; on the other hand, the fluorocarbon silane provides a low surface energy substance F, so that the material has two conditions of super hydrophobicity: coarse structures and low surface energy materials. The super-hydrophobic material disclosed by the invention has good and stable light conversion and super-hydrophobic properties, and can be better applied to the fields of polymer self-cleaning, dust prevention, light conversion and the like as a functional filler.)

1. A blue fluorescent carbon quantum dot modified super-hydrophobic material is characterized in that: comprises layered aluminosilicate with SiO modified on the surface₂Nanospheres, carbon quantum dots, and fluorosilicone copolymers.

2. A method for preparing the superhydrophobic material of claim 1, wherein: the method comprises the following steps:

step 1, firstly adding layered aluminosilicate into water, stirring for 2-3 h at 60-80 ℃, dissolving a modifier in the water, then mixing a modifier solution with the layered aluminosilicate solution, stirring for 2-3 h, carrying out centrifugal separation, taking a precipitate, drying in an oven, and then grinding and sieving to obtain the modified layered aluminosilicate;

step 2, dissolving citric acid and banana peel in water, adjusting the pH value of the solution to 7 by using ammonia water, placing the solution in a hydrothermal reaction kettle, reacting for 12 hours at 180 ℃, cooling to room temperature, centrifugally separating large particles, and freezing and vacuum-drying the supernatant to obtain blue fluorescent carbon quantum dots;

and 3, refluxing and stirring polyhydroxy silane, a silane coupling agent, an alcohol solvent, fluorocarbon silane, modified layered aluminosilicate and a carbon quantum dot solution under an acidic condition for reaction, drying in an oven, grinding and sieving to obtain the super-hydrophobic material.

3. The method of claim 2, wherein: in step 1, the layered aluminosilicate is selected from montmorillonite, talc or mica; the modifier is alkyl ammonium bromide selected from dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide; the ratio of the layered aluminosilicate to the modifier is 1: 3CEC, 1: 1.5CEC or 1: 2 CEC.

4. The method of claim 2, wherein: in the step 2, the dosage ratio of the citric acid to the banana peel to the water is 1 g: 1 g: 20 mL.

5. The method of claim 2, wherein: in the step 3, the mass ratio of the polyhydroxy silane, the silane coupling agent, the alcohol solvent, the fluorocarbon silane, the modified layered aluminosilicate to the carbon quantum dot solution is 3-3.6: 0.25-0.3: 25-30: 2-3: 4-6: 1-3; the acidic condition is pH 3-5.

6. The method of claim 2, wherein: in the step 3, the ratio of the carbon quantum dots to the modified layered aluminosilicate is 1: 0.1-0.01.

7. The method of claim 2, wherein: the reaction conditions of the reflux stirring in the step 3 are 60-80 ℃ and 9-13 hours.

8. The method of claim 2, wherein: in the step 3, the polyhydroxy silane is tetraethoxysilane or methyl orthosilicate; the silane coupling agent is selected from gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane or gamma-methacryloxypropyltrimethoxysilane; the fluorocarbon silane is selected from 1H,1H,2H, 2H-perfluorooctyltrimethoxysilane, 1H,2H, 2H-perfluorooctyltriethoxysilane or 1H,1H,2H, 2H-perfluorodecyltrimethoxysilane.

9. Use of the superhydrophobic material of claim 1 in the preparation of a functional filler.

Technical Field

The invention belongs to the technical field of hydrophobic materials, and particularly relates to a blue fluorescent carbon quantum dot modified super-hydrophobic material, and a preparation method and application thereof.

Background

The super-hydrophobic material has wide application prospect in production and life due to the unique wettability of the surface. In the aspect of the building field, the super-hydrophobic material is used for the building outer wall to endow the building outer wall with self-cleaning performance, so that the cleaning difficulty and the maintenance cost are greatly reduced; in the aspect of the ocean field, the super-hydrophobic coating is constructed on the surface of a net-shaped or porous material, the high-efficiency oil-water separation can be realized by utilizing the wettability difference of the coating on oil and water, and the method has important significance for environmental protection and resource recycling. Meanwhile, the super-hydrophobic material is coated on the surface of the outer shell of a ship, a submarine and the like, so that the resistance of the ship body in the water surface motion can be effectively reduced, the navigation speed is improved, and the metal of the outer shell is prevented from being corroded by seawater or attached by pollutants; in the clothing textile field, the super-hydrophobic coating is used on the surfaces of textiles and shoes, so that the clothing cleaning times can be reduced, and the rainproof and antifouling effects can be achieved in rainy days. The metal material is used as an important engineering material, and the super-hydrophobic coating is constructed on the surface of the metal material, so that the direct contact between corrosive liquid and the metal surface can be effectively reduced, moisture and microorganisms are isolated, and an excellent anti-corrosion effect is achieved; in daily life, severe safety accidents and economic losses are caused by ice coating on the surfaces of wires, industrial equipment, roads and the like caused by severe cold weather, and the surfaces of the superhydrophobic materials have the function of delaying ice formation or preventing ice adhesion. Therefore, the preparation and research of the super-hydrophobic material have great practical value. With the rapid development of modern industry and artificial intelligence, the single super-hydrophobicity is difficult to meet the use requirements of materials in severe environments and emerging fields. Therefore, when the super-hydrophobic material is designed and prepared, besides super-hydrophobicity, at least one function of repairability, stretchability, magnetism, transparency, electric conductivity, thermal conductivity, flame retardance and the like is given to the super-hydrophobic material, so that the service life of the material can be prolonged, and the application of the material in new fields of flexible electronics, rapid ice and snow melting, unmanned driving, transparent electrodes and the like can be widened.

Carbon nanomaterials such as nanodiamonds, fullerenes, carbon nanotubes, graphene sheets and carbon quantum dots, have been extensively studied for their unique properties and great potential in a variety of technical applications. Carbon quantum dots generally refer to carbon skeleton and surface functional groups less than 10 nm in sizeThe constituent nanomaterials having a carbonaceous skeleton, usually sp²Hybridized C = C, C-O, O-C = O and graphitic carbon, or sp²/sp³The surface of the carbon quantum dots usually contains active functional groups such as carboxyl (-COOH), amino (-NH) in addition to carbon element₂) Hydroxyl (-OH), and the like. The carbon quantum dots have the characteristics different from the traditional metal quantum dots, such as high light stability, good biomolecule compatibility, no light excitation wavelength dependence, simple and convenient preparation process, low cost and the like. In addition, the carbon quantum dots have rapid photoproduction electron transfer capability, are good electron acceptors and donors, have small particle size and molecular weight, and can be excited to generate upconversion fluorescence. In recent years, among the physicochemical properties of carbon quantum dots, their optical properties and functional properties have attracted increasing interest.

Zhai Chen et al in Chinese academy of sciences have studied the green glow carbon dot montmorillonite composite material, explore its application in LED optical field; the silicon dioxide-modified montmorillonite composite coating is prepared by the Shiyafang et al of the university of southern China through a physical blending mode, and the nano SiO on the surface of the coating₂The micro-nano composite structure is constructed together with micron-sized montmorillonite, and research shows that SiO is obtained₂The ratio to MMT was 1:1, with a WCA of 163.5 ° and a WSA of 4.3 °; although the research can slow down the agglomeration and sedimentation process of the nano powder by virtue of the good dispersibility of the montmorillonite in the organic component, the physical blending mode can cause the problems of uneven mixing and separation between the nano powder and the montmorillonite, poor adhesion between the silicon dioxide and the resin, abrasion and the like. At present, researchers have reported that the fluorescence property of carbon dots is applied to improve the light conversion efficiency of plants and increase the photosynthesis of the plants. Although the super-hydrophobic material and the carbon dots are widely applied, researches on mutual combination and synergistic action of the two materials are less, and particularly, the two materials are combined into the super-hydrophobic material and applied to a polymer matrix as a nano filler to realize the light conversion-super-hydrophobic double functions, and no literature report is found.

Disclosure of Invention

In view of the above prior artThe invention aims to provide a blue fluorescent carbon quantum dot modified super-hydrophobic material, which is prepared by modifying layered aluminosilicate through a modifier, and grafting SiO with different particle sizes on the modified layered aluminosilicate through a chemical bond in a hydrolysis copolycondensation mode₂Nanospheres and carbon quantum dots with smaller particle size, and the surface energy is improved by the fluorine-silicon copolymer, so that the nano-nanospheres and the carbon quantum dots have good and stable light conversion and super-hydrophobic properties, and can be used as a functional filler to be better applied to the fields of polymer self-cleaning, dust prevention, light conversion and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

a blue fluorescent carbon quantum dot modified super-hydrophobic material comprises layered aluminosilicate, wherein the surface of the layered aluminosilicate is modified with SiO₂Nanospheres, carbon quantum dots, and fluorosilicone copolymers.

The preparation method of the super-hydrophobic material comprises the following steps:

step 1, firstly adding layered aluminosilicate into water, stirring for 2-3 h at 60-80 ℃, dissolving a modifier in the water, then mixing a modifier solution with the layered aluminosilicate solution, stirring for 2-3 h, carrying out centrifugal separation, taking a precipitate, drying in an oven, and then grinding and sieving to obtain the modified layered aluminosilicate;

step 2, dissolving 1g of citric acid and 1g of banana peel in 20 mL of water, adjusting the pH value of the solution to 7 by using ammonia water, placing the solution in a hydrothermal reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, centrifuging to separate large particles, and carrying out freeze vacuum drying on the supernatant to obtain blue fluorescent carbon quantum dots;

and 3, refluxing and stirring polyhydroxy silane, a silane coupling agent, an alcohol solvent, fluorocarbon silane, modified layered aluminosilicate and a carbon quantum dot solution under an acidic condition for reaction, drying in an oven, grinding and sieving to obtain the super-hydrophobic material.

Further, in step 1, the layered aluminosilicate is selected from montmorillonite, talc or mica; the modifier is alkyl ammonium bromide selected from dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide; the ratio of the layered aluminosilicate to the modifier is 1: 3CEC, 1: 1.5CEC or 1: 2 CEC.

In the present invention, CEC (66.67 mmoL/100 g) is the cation exchange capacity of the layered aluminosilicate.

Preferably, the modifier is octadecyl trimethyl ammonium bromide, the layered aluminosilicate is montmorillonite, and the ratio of the montmorillonite to the modifier is 1: 3 CEC.

Further, in the step 3, the mass ratio of the polyhydroxy silane, the silane coupling agent, the alcohol solvent, the fluorocarbon silane, the modified layered aluminosilicate and the carbon quantum dot solution is 3-3.6: 0.25-0.3: 25-30: 2-3: 4-6: 1-3; the acidic condition is pH 3-5.

Further, the mass ratio of the carbon quantum dots to the modified layered aluminosilicate is 1: 0.1-0.01.

Further, the conditions of the reflux stirring reaction in the step 3 are 60-80 ℃ and 9-13 hours.

Further, in step 3, the polyhydroxy silane is Tetraethoxysilane (TEOS) or methyl orthosilicate (TMOS); the silane coupling agent is selected from gamma-aminopropyltriethoxysilane (KH-550), gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KH-560) or gamma-methacryloxypropyltrimethoxysilane (KH-570); the fluorocarbon silane is selected from 1H,1H,2H, 2H-Perfluorooctyltrimethoxysilane (PFOTS), 1H,2H, 2H-Perfluorooctyltriethoxysilane (PFOTS) or 1H,1H,2H, 2H-Perfluorodecyltrimethoxysilane (PFDTS).

The invention firstly utilizes a modifier to modify layered aluminosilicate so as to facilitate SiO during cohydrolysis₂The nanospheres and the carbon quantum dots can be uniformly distributed on the surface of the sheet layer. SiO of different particle sizes₂The nanospheres and the carbon dots with smaller particle sizes jointly construct a stable and rough micro-nano structure, and meanwhile, fluorocarbon silane provides a low-surface-energy substance F, so that the material has two conditions of super-hydrophobicity: coarse structures and low surface energy materials. The preparation method of the invention has controllable reaction and simple operation.

According to the invention, the banana peel which is a biomass waste is used as a source of the carbon quantum dots, so that the waste utilization is realized, the green and natural effects are achieved, the synthesized quantum dots have excellent quantum yield, the layered aluminosilicate modified by the quantum dots has a fluorescence characteristic, ultraviolet light can be converted into blue light, and the nano structure provided by the carbon quantum dots can improve the performance of the super-hydrophobic material.

The invention grafts SiO on the surface of the layered aluminosilicate in a chemical bond mode by a hydrolysis copolycondensation mode₂The nano sphere and the carbon quantum dot greatly improve the stability of the super-hydrophobic material; meanwhile, the fluorocarbon silane is hydrolyzed into silicon hydroxyl bonds (-Si-OH) and is combined with hydroxyl groups (-OH) on the layered aluminosilicate, so that the material has lower surface energy.

Has the advantages that: compared with the prior art, the invention has the following advantages:

(1) the invention firstly utilizes carbon point modification to prepare the super-hydrophobic material with the blue light function.

(2) The invention has the advantages of wide raw material source, utilization of biomass waste, low price and simple synthesis process.

(3) The super-hydrophobic material prepared by the invention has strong absorption in an ultraviolet region, and the ethanol solution of the super-hydrophobic material emits bright blue fluorescence under the irradiation of an ultraviolet lamp.

(4) The super-hydrophobic material prepared by the invention has excellent super-hydrophobic performance, the water contact angle is 168.7 +/-2 degrees, and the rolling angle is 4.3 +/-0.2 degrees.

Drawings

FIG. 1 is a Transmission Electron Micrograph (TEM) of a superhydrophobic material of example 1;

FIG. 2 is a Scanning Electron Micrograph (SEM) of the superhydrophobic material of example 1;

FIG. 3 is an infrared spectrum (FTIR) of the superhydrophobic material of example 1;

FIG. 4 is an X-ray diffraction pattern (XRD) of the superhydrophobic material of example 1;

FIG. 5 is an ultraviolet absorption spectrum (UV) of the superhydrophobic material of example 1;

FIGS. 6 and 7 are fluorescence spectra (FA) of the superhydrophobic material of example 1;

FIG. 8 is a static water contact angle test chart (WCA) of the superhydrophobic material of example 1;

FIG. 9 is a dynamic water contact angle test chart (WSA) of the superhydrophobic material of example 1.

Detailed Description

The technical solution of the present invention is further illustrated by the following examples.

The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified. The layered aluminosilicate may be sodium montmorillonite, talc, mica, etc.

Example 1

Step 1, the method for preparing the modified layered aluminosilicate is that 3 g of montmorillonite is added into deionized water, stirred for 3 hours at 80 ℃, then 0.8 g of modifier (octadecyl trimethyl ammonium bromide) is dissolved in the deionized water, and then the modifier solution and the layered aluminosilicate solution are mixed and stirred for 3 hours. And (4) carrying out centrifugal separation to obtain a precipitate, drying in an oven, grinding and sieving to obtain the modified montmorillonite.

And 2, weighing 1g of citric acid and 1g of banana peel, dissolving the citric acid and the banana peel in 20 mL of deionized water, adjusting the pH value of the solution to 7 by using ammonia water, placing the solution in a hydrothermal reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, centrifuging to separate large particles, freeze-drying the supernatant in vacuum to obtain blue fluorescent carbon quantum dots, and dissolving the carbon quantum dots in the deionized water to obtain the carbon quantum dot solution.

And 3, taking 0.3 g of KH-570, 3.4 g of TEOS, 28 g of isopropanol solvent and 5g of modified montmorillonite, adding 3 g of carbon quantum dot solution (the mass of the carbon quantum dots is 0.05 g) and 2.5 g of PFOTES, adjusting the pH to 4 by using 12 mol/L concentrated hydrochloric acid, adjusting the temperature to 60 ℃, carrying out reflux stirring, and stirring for 12 hours at the rotation speed of 500 r/min.

And 4, drying the solution in an oven (at the temperature of 50 ℃ for 24 hours), grinding and sieving the dried solution with a 100-mesh sieve to obtain the blue fluorescent carbon quantum dot modified super-hydrophobic material.

The Transmission Electron Microscope (TEM) is shown in FIG. 1, the modified layered aluminate has a obvious sheet structure, and SiO with the particle size of 10-20 nm is uniformly grafted on the surface of the modified layered aluminate₂The nanospheres and the carbon quantum dots with the particle size of 4-6 nm jointly form a rough surface with a micro-nano structure, and the light color part around the lamella is fluorine-silicon copolymer with low surface energy.

Scanning Electron Microscopy (SEM) As shown in FIG. 2, the sample showed a layered structure with montmorillonite exfoliated and a surface with SiO₂The grafting of nanospheres and carbon quantum dots presents a roughness phenomenon, consistent with the TEM results.

XRD analysis As shown in FIG. 3, the 001-plane second order diffraction peak 2 of original MMT is alwaysθThe angle is 5.83 degrees, the angle is intercalated, the angle is moved to 4.16 degrees in the small angle direction, the spacing is increased by 0.61 nm through calculation of a Bragg equation, the interlayer spacing of the initial montmorillonite is 1.51 nm through calculation, after the surface modification and the high-molecular chain segment intercalation of the montmorillonite, the montmorillonite is obviously deviated in the small angle direction, and the interlayer spacing is increased to 2.12 nm.

Mixing the prepared super-hydrophobic material modified by the blue fluorescent carbon quantum dots with potassium bromide (the mass ratio of the potassium bromide to the sample is 100: 1), grinding, tabletting, testing by using a Brookalpha II Fourier transform infrared spectrometer, and scanning the sample in the range of 4000-400 cm^-1. FIG. 4 shows the absorption peaks at 3628 cm for different functional groups at different wavelengths^-1Stretching vibration of O-H bond in octahedral skeleton; 3456 cm^-1 、1643 cm^-1The absorption peak is the stretching vibration and bending vibration of H-O-H bond caused by interlayer crystal water or adsorbed water of the layered aluminosilicate; 760 to 840 cm^-1 Si-C，1090 cm^-1A strong Si-O symmetrical stretching vibration peak exists; is located at 1205-1440 cm^-1、656 cm^-1、780 cm^-1is-CF₂、-CF₃C-F absorption peak; 1450 cm^-1Is C-N stretching vibration peak, 3345 cm^-1Is an N-H stretching vibration peak; 1250 cm^-1、1180 cm^-1And 1080 cm^-1is-COO, C-OH, C-O-C functional group; 1700 cm^-1Is the absorption peak of C = O, 1632cm^-1C = C, 2975-2899 cm^-1Is represented by-CH₃、-CH₂The telescopic vibration peak can be obtained in a comprehensive way, and the successfully prepared material hasAnd the blue fluorescent carbon quantum dot modified super-hydrophobic material.

An ultraviolet/visible/near-infrared spectrophotometer (Cary 5000) is used for testing the 200-800 nm absorption spectrum of the blue fluorescent carbon quantum dot modified super-hydrophobic material solid powder, as shown in figure 5, strong absorption exists in an ultraviolet region of 200-400 nm, the wavelength of 260-276 nm is mainly due to pi-pi transition of C = C atom, and a wide and flat absorption peak at 320 nm is caused by N-pi transition of electrons of C = O/C = N atom. The material is dissolved in ethanol solution and placed in a cuvette, and under an ultraviolet lamp, obvious blue fluorescence can be observed, which is mainly due to the fact that carbon quantum dots with fluorescence properties are successfully grafted on the surface of the layered aluminosilicate. Secondly, the fluorescence effect of the material is tested by using a molecular fluorescence spectrometer (LS-50B), and fig. 6 shows that the material has stronger ultraviolet absorption and the ultraviolet test result is consistent under the emission wavelength of 430 nm; FIG. 7 shows that the fluorescence with the strongest fluorescence effect at 360 nm is shown at different excitation wavelengths (300 nm, 320 nm, 340 nm, 360 nm), and the maximum emission wavelength is 430 nm.

And testing static and dynamic water contact angles of the blue fluorescent carbon quantum dot modified super-hydrophobic material. Firstly, fixing a double-sided adhesive tape on one surface of a glass slide, spreading 1g of blue fluorescent carbon quantum dot modified super-hydrophobic material on the double-sided adhesive tape, blowing off redundant samples by using an ear washing ball, and testing the contact angle of the samples by using deionized water. When the contact angle was measured using a droplet shape analyzer (DSA30S), the volume of the droplet was 10 μ L. The surface of the sample was measured at 3 different positions, and the average value was taken as the measurement value. FIG. 8 shows the super-hydrophobic property of the material, and the static water contact angle reaches 168.7 +/-2 degrees. FIG. 9 is a dynamic water contact angle measurement with a dynamic contact angle measurement angle of 4.3 + -0.2 deg.. The test result shows that the super-hydrophobic material has excellent super-hydrophobic performance due to the rough surface micro-nano structure and the surface modification of the fluorine-silicon copolymer.

Example 2

Step 1, the method for preparing the modified layered aluminosilicate comprises the steps of firstly adding 3 g of montmorillonite into deionized water, stirring for 3 h at 80 ℃, then dissolving 0.4 g of modifier (cetyl trimethyl ammonium bromide) in the deionized water, then mixing the modifier solution and the layered aluminosilicate solution, and stirring for 3 h. And (4) carrying out centrifugal separation to obtain a precipitate, drying in an oven, grinding and sieving to obtain the modified montmorillonite.

And 2, weighing 1g of citric acid and 1g of banana peel, dissolving the citric acid and the banana peel in 20 mL of deionized water, adjusting the pH value of the solution to 7 by using ammonia water, placing the solution in a hydrothermal reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, centrifuging to separate large particles, freeze-drying supernatant in vacuum to obtain blue fluorescent carbon quantum dots, and dissolving the carbon quantum dots in the deionized water to obtain the carbon quantum dot solution.

And 3, taking 0.28 g of KH-550, 3 g of TEOS, 25 g of isopropanol solvent and 5g of modified montmorillonite, adding 2 g of carbon quantum dot solution (the mass of the carbon quantum dots is 0.005 g) and 3 g of PFDTS, adjusting the pH to 4 by using 12 mol/L concentrated hydrochloric acid, adjusting the temperature to 60 ℃, carrying out reflux stirring, and stirring for 12 hours at the rotation speed of 500 r/min.

And 4, drying the solution in an oven (at the temperature of 50 ℃ for 24 hours), grinding and sieving the dried solution with a 100-mesh sieve to obtain the blue fluorescent carbon quantum dot modified super-hydrophobic material.

Example 3

Step 1, the method for preparing the modified layered aluminosilicate comprises the steps of firstly adding 3 g of talcum into deionized water, stirring for 3 h at 60 ℃, then dissolving 0.35 g of modifier (dodecyl trimethyl ammonium bromide) in the deionized water, then mixing the modifier solution and the layered aluminosilicate solution, and stirring for 3 h. And (4) carrying out centrifugal separation to obtain a precipitate, drying in an oven, grinding and sieving to obtain the modified talc.

And 2, weighing 1g of citric acid and 1g of banana peel, dissolving the citric acid and the banana peel in 20 mL of deionized water, adjusting the pH value of the solution to 7 by using ammonia water, placing the solution in a hydrothermal reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, centrifuging to separate large particles, freeze-drying supernatant in vacuum to obtain blue fluorescent carbon quantum dots, and dissolving the carbon quantum dots in the deionized water to obtain the carbon quantum dot solution.

And 3, adding 3 g of carbon quantum dot solution (the mass of the carbon quantum dots is 0.01 g) and 3 g of PFOTS into 0.25 g of KH-560, 3.6 g of TEOS, 30 g of isopropanol solvent and 6 g of modified talc, adjusting the pH to 5 by using 12 mol/L concentrated hydrochloric acid, adjusting the temperature to 60 ℃, carrying out reflux stirring, and stirring for 12 hours at the rotation speed of 500 r/min.

And 4, drying the solution in an oven (at the temperature of 50 ℃ for 24 hours), grinding and sieving the dried solution with a 100-mesh sieve to obtain the blue fluorescent carbon quantum dot modified super-hydrophobic material.

Example 4

Step 1, the method for preparing the modified layered aluminosilicate comprises the steps of firstly adding 3 g of montmorillonite into deionized water, stirring for 3 h at 80 ℃, then dissolving 1g of modifier (octadecyl trimethyl ammonium bromide) in the deionized water, then mixing the modifier solution and the layered aluminosilicate solution, and stirring for 3 h. And (4) carrying out centrifugal separation to obtain a precipitate, drying in an oven, grinding and sieving to obtain the modified montmorillonite.

And 2, weighing 1g of citric acid and 1g of banana peel, dissolving the citric acid and the banana peel in 20 mL of deionized water, adjusting the pH value of the solution to 7 by using ammonia water, placing the solution in a hydrothermal reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, centrifuging to separate large particles, freeze-drying supernatant in vacuum to obtain blue fluorescent carbon quantum dots, and dissolving the carbon quantum dots in the deionized water to obtain the carbon quantum dot solution.

And 3, adding 0.3 g of KH-570, 3.4 g of TEOS, 28 g of isopropanol solvent and 5g of modified montmorillonite into 3 g of carbon quantum dot solution (the mass of the carbon quantum dots is 0.05 g) and 2.5 g of PFOTES, adjusting the pH to 5 by using 12 mol/L concentrated hydrochloric acid, adjusting the temperature to 80 ℃, carrying out reflux stirring, and stirring for 9 hours at the rotation speed of 500 r/min.

And 4, drying the solution in an oven (at the temperature of 50 ℃ for 24 hours), grinding and sieving the dried solution with a 100-mesh sieve to obtain the blue fluorescent carbon quantum dot modified super-hydrophobic material.

Example 5

Step 1, the method for preparing the modified layered aluminosilicate comprises the steps of firstly adding 3 g of montmorillonite into deionized water, stirring for 2h at 60 ℃, then dissolving 0.2 g of modifier (octadecyl trimethyl ammonium bromide) in the deionized water, then mixing the modifier solution and the layered aluminosilicate solution, and stirring for 2 h. And (4) carrying out centrifugal separation to obtain a precipitate, drying in an oven, grinding and sieving to obtain the modified montmorillonite.

And 2, weighing 1g of citric acid and 1g of banana peel, dissolving the citric acid and the banana peel in 20 mL of deionized water, adjusting the pH value of the solution to 7 by using ammonia water, placing the solution in a hydrothermal reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, centrifuging to separate large particles, freeze-drying supernatant in vacuum to obtain blue fluorescent carbon quantum dots, and dissolving the carbon quantum dots in the deionized water to obtain the carbon quantum dot solution.

And 3, adding 0.3 g of KH-570, 3.4 g of TEOS, 28 g of isopropanol solvent and 5g of modified montmorillonite into 3 g of carbon quantum dot solution (the mass of the carbon quantum dots is 0.05 g) and 2.5 g of PFOTES, adjusting the pH to 3 by using 12 mol/L concentrated hydrochloric acid, adjusting the temperature to 80 ℃, carrying out reflux stirring, and stirring for 13 hours at the rotation speed of 500 r/min.

And 4, drying the solution in an oven (at the temperature of 50 ℃ for 24 hours), grinding and sieving the dried solution with a 100-mesh sieve to obtain the blue fluorescent carbon quantum dot modified super-hydrophobic material.