Method for preparing photocatalytic material by using amphiphilic agricultural waste cellulose loaded CuInSnS QDs composite nanoparticles and application thereof

Abstract

The application discloses a method for preparing a photocatalytic material by using a two-fiber cellulose loaded CuInSnS QD composite nanoparticle. N 2halogenated hydrocarbon reaction N-allyl-4-alkyl pyridine iminium is obtained, the N-allyl-4-alkyl pyridine iminium functional monomer is modified by two-fiber etherification in the alkali urea treated cellulose homogeneous system, and the two-fiber cellulose is obtained by regeneration; the two-fiber cellulose is dissolved in the DMAc / LiCl system again, and is used for loading photocatalytic nanoparticles, and through a hydrothermal reaction, finally, the two-fiber cellulose loaded CuInSnS QD composite of corn straw pith parenchyma cells is realized; the prepared composite material is light in texture, has a porous structure, good hydrophilicity and adsorbability, has a high-efficiency removing and killing effect on tinea pedis pathogenic bacteria under visible light irradiation, and further develops an application field of the corn straw pith, so that the environment-friendly and renewable green biological material is efficiently utilized.

Description

TECHNICAL FIELD

[0001] The application relates to a gallium-based liquid metal nanosphere in-situ modified by loading cuprous sulfide after two-phase modification of corn straw as a cellulose raw material, and a photocatalytic material is obtained, the composite has excellent antibacterial performance, and belongs to the technical field of natural polymer modified materials. BACKGROUND

[0002] With the rapid development of industry and the rapid expansion of population, environmental pollution is becoming increasingly serious, which creates favorable conditions for the survival and reproduction of various harmful bacteria and fungi. Therefore, the research and application of antibacterial materials are extremely important.

[0003] Nowadays, the main types of antibacterial agents include natural antibacterial agents, organic antibacterial agents, inorganic antibacterial agents and the like. The natural antibacterial agents have good biocompatibility, are non-toxic and harmless, but their application is limited due to poor heat resistance and short drug efficacy; the organic antibacterial agents have a wide antibacterial range but are toxic and easy to hydrolyze; and the inorganic antibacterial agents have good heat resistance, low toxicity and do not produce drug resistance compared with other antibacterial agents. Among the various antibacterial agents, the inorganic antibacterial agents are mainly composed of micro-nano metal oxides and sulfides. These effective substances can not only decompose various organic substances by using light energy, but also can kill bacteria, resist bacteria and effectively decompose the residues and toxins in the bacteria through ion penetration, physical contact or active oxygen conversion. Studies have shown that common metal oxides (sulfides) include TiO2, ZnO and CdS. The main antibacterial mechanism is that under visible light or ultraviolet light irradiation, high-reactivity substances are generated through photocatalysis, and then the substances react with organic substances in microorganisms, so as to realize antibacterial effect. Although TiO2 and ZnO are commonly used antibacterial materials, TiO2 has poor visible light absorption, weak environmental adaptability and low photocatalytic activity, which seriously affects its use value. Although ZnO is active in the ultraviolet absorption band and can make the band gap narrow after doping, the carriers are easy to fall into traps, resulting in chemical transformation of electrons or holes and weakening of the killing performance. The presence of Cd in CdS limits its wide application due to environmental pollution. The latest research shows that Ⅰ-Ⅲ-Ⅵ QDs and their derivatives have the characteristics of variable band gap with composition, full visible light coverage, high efficiency, excellent stability and non-toxicity, and thus are expected to become ideal environmental protection materials to replace traditional cadmium-based and lead-based quantum dots. 2+

[0004] ​Corn stalk (CS) is considered to be one of the most abundant renewable agricultural wastes in the world. CS is mainly composed of straw skin and straw core, which have different tissues, cell morphology and chemical composition. The corn stalk core is mainly composed of solid residues such as fiber cells, parenchyma cells, vascular bundles, etc. Compared with fiber cells, the straw core parenchyma cell has a thin cell wall, a short growth cycle, and a small molecular weight, so it has the advantages of loose structure, high reaction accessibility, specific surface area, softness, good biocompatibility, etc. Through chemical composition analysis, corn stalk core contains cellulose, hemicellulose and lignin, and the carbohydrate content of corn stalk core obtained by peeling is high (45% cellulose and 32.2% hemicellulose), which shows that the cellulose molecular chain is rich in oxygen-containing functional groups such as hydroxyl groups, which provides good conditions for further chemical modification (such as esterification, etherification, graft copolymerization, modification of amphiphilic functional monomers, etc.), making it an ideal green functional carrier material. Therefore, by modifying the amphiphilic functional monomer of the parenchyma cell cellulose to prepare pyridinium salt cellulose ether, the antibacterial value is given, which is a promising biomass carrier material in the future.

[0005] In combination with the problem of microbial water pollution caused by modern industry, the application details the process flow of preparing amphiphilic cellulose in situ photocatalytic composite nanoparticles with corn stalk core as plant raw material, as an antibacterial agent for inhibiting athlete's foot pathogenic bacteria. The comprehensive utilization efficiency of corn stalk core resources is improved, and the application range of corn stalk core is widened. SUMMARY

[0006] There is still a big gap in the technology and means for efficiently treating athlete's foot pathogenic bacteria using waste biomass as a natural polysaccharide polymer source, and the research and industrial utilization based on the functionalization modification of corn stalk core cellulose are not perfect. At the same time, how to construct a green and environmentally friendly photocatalytic semiconductor nanocomposite material to form a morphologically stable material in a humid environment, and has the function of efficiently converting light energy to degrade pathogenic bacteria is one of the current research hotspots. Therefore, the application provides a preparation method of corn stalk core parenchyma cell amphiphilic modified cellulose loaded with sulfur copper tin indium quantum dots, which uses the resource-rich and underdeveloped corn stalk core as raw material, through crushing and screening, directional cellulose extraction and alkali urea dissolution, and at the same time, S N 2halogenated hydrocarbon reaction to obtain N-allyl-4-alkyl pyridinium chloride, and the N-allyl-4-alkyl pyridinium chloride functional monomer is subjected to amphiphilic etherification modification in the alkali urea treated cellulose homogeneous system, and regenerated to obtain amphiphilic cellulose, which is used as a functional carrier. Amphiphilic cellulose is dissolved in a DMAc / LiCl system again for loading photocatalytic nanoparticles, and through hydrothermal reaction, the corn stalk core parenchyma cell amphiphilic cellulose loaded with CuInSnS QDs composite is finally realized, which further develops the application field of corn stalk core, and makes the environmentally friendly and renewable green biological material be efficiently utilized.

[0007] The specific steps of the method are as follows:

[0008] (1) 4-alkyl pyridine is dissolved in anhydrous ether-acetonitrile mixture to obtain a mixture with a concentration of 0.5-5 mol / L, chloropropene is added and mixed, and then the mixture is reacted at 20-50°C under a nitrogen atmosphere for 5-15 h. After the reaction is completed, an excess of ether or acetonitrile is added to precipitate the product, the precipitate is collected and washed with anhydrous ether or anhydrous acetonitrile for 3-5 times, and then freeze-dried to obtain N-allyl-4-alkyl pyridinium chloride;

[0009] The anhydrous ether-acetonitrile mixture is prepared by mixing anhydrous ether and acetonitrile at a volume ratio of 0.1-1:1, and the molar ratio of chloropropene to 4-alkyl pyridine is 1:1-1.5;

[0010] (2) The dried corn stalk is peeled, ground and sieved to obtain a 150-500 mesh stalk powder. The stalk powder is placed in dimethyl sulfoxide containing 3-15% (by volume) tert-butyl hydroperoxide, and reacted at 30-90°C for 0.5-5 h to remove lignin and hemicellulose. After the reaction is completed, the solid-liquid separation is performed, the solid is washed with water, and then naturally air-dried to obtain corn stalk parenchyma cellulose, wherein the mass volume concentration of the stalk powder in the reaction system is 5-12%;

[0011] Under stirring, the corn stalk parenchyma cellulose is placed in a tetrabutylammonium hydroxide-amino urea aqueous solution at -30--10°C, the gas bubbles in the liquid are removed by centrifugation, and then N-allyl-4-alkyl pyridinium chloride is added. The corn stalk parenchyma cellulose is modified by stirring at 50-90°C for 2-7 h. The modified cellulose is collected and added with an ethanol solution with a volume concentration of 10-95% for regeneration. Then, the regenerated cellulose is washed with water until neutral, and then freeze-dried to obtain amphiphilic cellulose. The amphiphilic cellulose is added to N,N-dimethylacetamide, reacted at 60-140°C for 1-3 h, then lithium chloride is added, and reacted at 50-90°C for 1-3 h. After the reaction is completed, the system is sealed and cooled, and then reacted at 2-6°C for 3-24 h to obtain an amphiphilic cellulose solution;

[0012] The concentration of the corn stalk parenchyma cellulose in the tetrabutylammonium hydroxide-amino urea aqueous solution is 0.01-0.1 g / mL. The mass volume concentration of tetrabutylammonium hydroxide in the tetrabutylammonium hydroxide-amino urea aqueous solution is 2.5-6.0%, and the mass volume concentration of amino urea is 8.0-25.0%. 1-2.5 mol of N-allyl-4-alkyl pyridinium chloride is added per mole of corn stalk parenchyma cellulose. The mass volume ratio g:mL of the amphiphilic cellulose to N,N-dimethylacetamide is 4-10%, and the mass volume ratio g:mL of lithium chloride to N,N-dimethylacetamide is 6-10%;

[0013] (3) In(NO3)3∙4.5H2O and SnCl4 were added to N,N-dimethylacetamide (DMAc) containing 0.01~0.07mmol / mL CuCl2 and ultrasonically dispersed. Then, the amphiphilic cellulose solution was added to the dispersion and mixed evenly to obtain a mixture. The mixture was added dropwise to an aqueous solution of carbon disulfide and hydrothermally reacted at 80~260℃ for 1~72 h. After the reaction was completed, the solid and liquid were separated, and the solid product was washed and freeze-dried to obtain the photocatalytic material.

[0014] The In 3+ With Cu 2+ The molar ratio is 2.16:0.722, Sn 4+ With Cu 2+ The molar ratio is 1.01:0.722, S 2- and Cu 2+ The molar ratio is 3:0.722.

[0015] Another objective of this invention is to apply the photocatalytic material prepared by the above method to the photocatalytic inhibition of Trichophyton rubrum (… Trichophyton rubrum ), Trichophyton mentagrophytes ( Trichophyton mentagrophytes )middle.

[0016] The beneficial effects of the present application are: using agricultural solid waste-corn stalk as a natural polymer source, a series of treatment steps are used to successfully prepare composite nanoparticles with excellent photocatalytic performance. This method not only innovatively converts waste into valuable functional materials, but also provides an effective way to solve the problem of tinea fungus. The corn stalks discarded by farmers are crushed, screened, directional cellulose is extracted, and an alkali-urea solution is obtained. The purpose is to break the hydrogen bonds between the cellulose molecules, so that the cellulose exists in the form of uniform distribution chain, and the reaction accessibility of the cellulose is improved. In this way, the pyridinium functional monomer can be modified by amphiphilic ether in the alkali-urea treated cellulose homogeneous system, and the amphiphilic cellulose with good amphiphilicity and photocatalytic performance is regenerated. Then, the photocatalytic particles are fixed on the cellulose through electrostatic interaction. In(NO3)3·4.5H2O, SnCl4 and CuCl2 are added to the amphiphilic cellulose solution and mixed together, and then regenerated in carbon disulfide liquid to form composite nanoparticles. The adsorption of pyridinium functional monomer and the blocking effect of DMAc reduce the combination speed of sulfur ions and copper ions, so that CuInSnS QDs are uniformly distributed on the surface of amphiphilic cellulose to form composite particles. This structure not only reduces the interface defects and charge recombination, but also shortens the charge transport path, provides more surface active sites, thereby promoting the extraction of minority carriers and charge transfer, and finally enhancing the photocatalytic performance of the composite. At the same time, this composite material has the advantages of low carrier cost, easy to obtain, non-toxic, environmentally friendly, etc. The realization of this composite material provides a new way for the high value-added utilization of corn stalks. This method not only reduces the pollution of agricultural waste to the environment, but also converts them into valuable resources, promoting sustainable development. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 HRTEM image of the photocatalytic material prepared in Example 1;

[0018] Figure 2 HRTEM image of the photocatalytic material prepared in Example 2;

[0019] Figure 3 HRTEM image of the photocatalytic material prepared in Example 3. DETAILED DESCRIPTION

[0020] The present application will be further described in conjunction with the examples below, but the scope of protection of the present application is not limited to the content described. Example 1

[0021] (1) 4-alkyl pyridine is dissolved in anhydrous ethyl ether-acetonitrile mixture (volume ratio is 0.1:1) to prepare a mixture with a concentration of 0.5 mol / L, chloroacrylene (molar ratio of chloroacrylene to 4-alkyl pyridine is 1:1) is added and mixed, and then the mixture is reacted at 20°C under nitrogen atmosphere for 15 hours. After the reaction is completed, excess ethyl ether is added to precipitate, and the precipitate is collected and washed with anhydrous ethyl ether for 3 times. After freeze-drying, N-allyl-4-alkyl pyridinium chloride is obtained;

[0022] (2) The dried corn stalk is peeled, ground and sieved to obtain 150-mesh stalk powder. The stalk powder is put into dimethyl sulfoxide containing 3% tert-butyl hydroperoxide and reacted at 30°C for 0.5 hours to remove lignin and hemicellulose. After solid-liquid separation, the solid is washed with water and naturally air-dried to obtain corn stalk parenchyma cellulose. The mass-volume concentration of the stalk powder in the reaction system is 5%;

[0023] Under mechanical stirring, the corn stalk parenchyma cellulose is put into a tetrabutylammonium hydroxide-amino urea aqueous solution at -30°C (the mass-volume concentration of tetrabutylammonium hydroxide is 2.5%, and the mass-volume concentration of amino urea is 8.0%). The concentration of the corn stalk parenchyma cellulose is 0.01 g / mL. The gas bubbles in the liquid are removed by centrifugation. Then, N-allyl-4-alkyl pyridinium chloride is added at a proportion of 1 mol per mole of corn stalk parenchyma cellulose. The mixture is placed in a constant-temperature water bath and stirred at 50°C for 7 hours. After the modification is completed, the modified cellulose is collected. 10% ethanol solution is added to regenerate the modified cellulose. Then, the regenerated cellulose is washed with water until it is neutral. After freeze-drying, amphiphilic cellulose is obtained;

[0024] The amphiphilic cellulose is added to N,N-dimethylacetamide. After reacting at 60°C for 3 hours, lithium chloride is added. After reacting at 50°C for 3 hours, the reaction is completed. After sealing and cooling, the mixture is reacted at 2°C for 15 hours to obtain an amphiphilic cellulose solution. The mass-volume ratio g:mL of the amphiphilic cellulose to N,N-dimethylacetamide is 4%, and the mass-volume ratio g:mL of lithium chloride to N,N-dimethylacetamide is 6%;

[0025] (3) In(NO3)3·4.5H2O and SnCl4 are added to DMAc containing 0.01 mmol / mL CuCl2 and ultrasonically dispersed. Then, the amphiphilic cellulose solution is added to the dispersion to obtain a mixture. The mixture is added dropwise to an aqueous carbon disulfide solution. The molar ratio of In 3+ to Cu 2+ is 2.16:0.722, the molar ratio of Sn 4+ to Cu 2+ is 1.01:0.722, and the molar ratio of S 2- to Cu2+ The molar ratio of the two is 3:0.722. After hydrothermal reaction at 80°C for 10h, solid-liquid separation, washing the solid product with water, and freeze-drying, the amphiphilic agricultural waste cellulose loaded CuInSnS QDs composite nanoparticle photocatalytic material is obtained, which is gray-black, porous structure, and light in texture. The BET specific surface area of the photocatalytic material is 277cm 2 / g; the TEM image of the photocatalytic material is shown in Figure 1 As can be seen from the figure, the dark area is nanoparticles, and the average diameter of the nanoparticles is 7.90nm;

[0026] (4) The antibacterial performance of the photocatalytic material was detected by the plate coating method, which was carried out according to the method in the standard GB 215512-2010. After irradiation by 500mW / cm 2 LED for 60min, the inhibition rate of the photocatalytic material of the present embodiment on Trichophyton rubrum was 98.6%, and the inhibition rate on Trichophyton tonsurans was 96.3%. Example 2

[0027] (1) 4-alkyl pyridine was dissolved in anhydrous ethyl ether-acetonitrile mixture (volume ratio of 0.5:1) to prepare a mixture with a concentration of 2.5mol / L. After adding chloroacrylate (the molar ratio of chloroacrylate to 4-alkyl pyridine was 1:1.3) and mixing, the mixture was reacted at 35°C under nitrogen atmosphere for 10h. After the reaction was completed, excess acetonitrile was added to precipitate the product. The precipitate was collected and washed with anhydrous acetonitrile for 4 times, and then freeze-dried to obtain N-allyl-4-alkyl pyridinium chloride;

[0028] (2) The dried corn stalks were peeled, ground and sieved to obtain 300 mesh stalk powder. The stalk powder was placed in a dimethyl sulfoxide solution containing 9% tert-butyl hydroperoxide and reacted at 60°C for 3h to remove lignin and hemicellulose. After solid-liquid separation, the solid was washed with water and naturally air-dried to obtain corn stalk parenchyma cellulose. The mass-volume concentration of the stalk powder in the reaction system was 8%;

[0029] Under mechanical stirring, the corn stalk parenchyma cellulose was placed in a tetrabutylammonium hydroxide-amino urea aqueous solution at -20°C (the mass-volume concentration of tetrabutylammonium hydroxide was 4.5%, and the mass-volume concentration of amino urea was 16.0%). The concentration of the corn stalk parenchyma cellulose was 0.05g / mL. The gas bubbles in the liquid were removed by centrifugation. Then, N-allyl-4-alkyl pyridinium chloride was added at a ratio of 2mol per mol of corn stalk parenchyma cellulose. The mixture was placed in a constant-temperature water bath and stirred at 70°C for 4.5h. After the modification was completed, the modified cellulose was collected. 90% ethanol solution was added to regenerate the modified cellulose. Then, the regenerated cellulose was washed with water until it was neutral. Finally, the freeze-dried product was obtained as the amphiphilic cellulose;

[0030] The amphiphilic cellulose is added into N,N-dimethylacetamide, reacted at 100℃ for 2h, then lithium chloride is added, reacted at 70℃ for 2h, after the reaction is completed, sealed and cooled, reacted at 4℃ for 10h, to obtain an amphiphilic cellulose solution, wherein the mass-volume ratio g:mL of the amphiphilic cellulose to N,N-dimethylacetamide is 7%, and the mass-volume ratio g:mL of lithium chloride to N,N-dimethylacetamide is 8%;

[0031] (3) In(NO3)3·4.5H2O and SnCl4 are added into DMAc containing 0.04 mmol / mL CuCl2 and ultrasonically dispersed, then the amphiphilic cellulose solution is added into the dispersion and mixed uniformly to obtain a mixture, the mixture is added dropwise into an aqueous carbon disulfide solution, and hydrothermal reaction is carried out at 170℃ for 36h, after the reaction is completed, solid-liquid separation is carried out, and the solid product is washed and freeze-dried, to obtain a photocatalytic material, which is gray-black, has a porous structure and light texture, and has a BET specific surface area of 508 cm2 / g; the TEM image of the photocatalytic material is shown in 2 Figure 2 It can be seen from the figure that the dark area is nanoparticles, and the average diameter of the nanoparticles is 7.11 nm;

[0032] (4) The antibacterial performance of the photocatalytic material is detected by a plate coating method, and the plate coating method is carried out according to the method in standard GB 215512-2010, and the light intensity of the 500mW / cm 2 After irradiation for 60min, the inhibition rate of the photocatalytic material of the present embodiment on Trichophyton rubrum is 100%, and the inhibition rate on Trichophyton tonsurans is 99.9%. Example 3

[0033] (1) 4-alkylpyridine is dissolved in a mixture of anhydrous diethyl ether-acetonitrile (volume ratio is 1:1) to obtain a mixture with a concentration of 5mol / L, chloroallyl (molar ratio of chloroallyl to 4-alkylpyridine is 1:1.5) is added into the mixture and mixed uniformly, then reaction is carried out at 50℃ under a nitrogen atmosphere for 5h, after the reaction is completed, an excess of diethyl ether is added to precipitate, the precipitate is collected and washed with anhydrous diethyl ether for 4 times, and freeze-drying is carried out, to obtain N-allyl-4-alkylpyridinium chloride;

[0034] (2) The air-dried corn stalk is peeled, ground and sieved to obtain 500-mesh stalk powder, the stalk powder is put into dimethyl sulfoxide containing 15% tert-butyl hydroperoxide, and reaction is carried out at 90℃ for 1h to remove lignin and hemicellulose, then solid-liquid separation is carried out, the solid is washed with water, and natural air-drying is carried out, to obtain corn stalk parenchymal cell cellulose, wherein the mass-volume concentration of the stalk powder in the reaction system is 10%;

[0035] ​Under mechanical stirring, the corn straw pith parenchymal cell cellulose was placed in a tetrabutylammonium hydroxide-aminoform hydroxide aqueous solution at -10℃, wherein the corn straw pith parenchymal cell cellulose concentration was 0.1 g / mL, the bubbles in the liquid were removed by centrifugation, then N-allyl-4-alkyl pyridinium chloride was added in a proportion of 2.5 mol per mol of corn straw pith parenchymal cell cellulose, the mixture was placed in a constant temperature water bath at 90℃ and stirred for 2 h, after the modification was completed, the modified cellulose was collected, 50% ethanol solution was added to regenerate the modified cellulose, then the regenerated cellulose was washed with water until neutral, and freeze-drying was performed, thereby obtaining the amphiphilic cellulose;

[0036] The amphiphilic cellulose was added into N,N-dimethylacetamide, reacted at 140℃ for 1 h, then lithium chloride was added, reacted at 90℃ for 1 h, after the reaction was completed, the mixture was sealed and cooled, reacted at 6℃ for 5 h, thereby obtaining an amphiphilic cellulose solution, wherein the mass-volume ratio g:mL of the amphiphilic cellulose to N,N-dimethylacetamide was 10%, and the mass-volume ratio g:mL of lithium chloride to N,N-dimethylacetamide was 9%;

[0037] (3) In(NO3)3·4.5H2O and SnCl4 were added into DMAc containing 0.04 mmol / mL CuCl2 and ultrasonically dispersed, then the amphiphilic cellulose solution was added into the dispersion and mixed uniformly to obtain a mixture, the mixture was added dropwise into an aqueous carbon disulfide solution, and hydrothermal reaction was performed at 250℃ for 5 h, after the reaction was completed, solid-liquid separation was performed, the solid product was washed and freeze-dried, thereby obtaining a photocatalytic material, which was gray-black, had a porous structure and a light texture, and had a BET specific surface area of 398 cm 2 / g; the TEM image of the photocatalytic material is shown in Figure 3 As can be seen from the image, the dark area is nanoparticles, and the average diameter of the nanoparticles is 8.6 nm;

[0038] (4) The antibacterial performance of the photocatalytic material was detected by a plate coating method, and the plate coating method was performed according to the method in standard GB 215512-2010, and the light intensity of the 500 mW / cm 2 After the LED irradiation for 60 min, the inhibition rate of the photocatalytic material of the present embodiment on Trichophyton rubrum was 99.8%, and the inhibition rate on Microsporum audouini was 98.5%.

Claims

1. A method for preparing a photocatalytic material by using an amphiphilic agricultural waste cellulose loaded CuInSnS QDs composite nanoparticle, characterized in that The following steps are taken: (1) 4-alkyl pyridine is dissolved in anhydrous ethyl ether-acetonitrile mixture to obtain a mixture with a concentration of 0.5-5 mol / L, chloropropene is added and mixed, and then the mixture is reacted at 20-50℃ under a nitrogen atmosphere for 5-15 h. After the reaction is completed, an excess of ethyl ether or acetonitrile is added to precipitate, the precipitate is collected and washed with anhydrous ethyl ether or anhydrous acetonitrile for 3-5 times, and then freeze-drying is performed to obtain N-allyl-4-alkyl pyridinium chloride; (2) Under stirring, corn stalk pith parenchymal cellulose is placed in a tetrabutylammonium hydroxide-aminoform hydroxide aqueous solution at -30 to -10℃, and then centrifugation is performed to remove bubbles in the liquid. Then, N-allyl-4-alkyl pyridinium chloride is added, and the corn stalk pith parenchymal cellulose is modified by stirring at 50-90℃ for 2-7 h. The modified cellulose is collected and then regenerated by adding an ethanol solution with a volume concentration of 10-95%. Then, the regenerated cellulose is washed with water until neutral, and then freeze-drying is performed to obtain amphiphilic cellulose; The amphiphilic cellulose is added to N,N-dimethylacetamide, and then the mixture is reacted at 60-140℃ for 1-3 h. Then, lithium chloride is added, and the mixture is reacted at 50-90℃ for 1-3 h. After the reaction is completed, the mixture is sealed and cooled, and then reacted at 2-6℃ for 3-24 h to obtain an amphiphilic cellulose solution; (3) In(NO3)3·4.5H2O and SnCl4 are added to N,N-dimethylacetamide containing 0.01-0.07 mmol / mL CuCl2, and then ultrasonic dispersion is performed. Then, the amphiphilic cellulose solution is added to the dispersion to obtain a mixture. The mixture is added dropwise to a carbon disulfide aqueous solution, and then hydrothermal reaction is performed at 80-260℃ for 1-72 h. After the reaction is completed, solid-liquid separation is performed, and then the solid product is washed and freeze-dried to obtain a photocatalytic material.

2. The method of claim 1, wherein the preparation of the photocatalytic material is carried out by using the amphiphilic agricultural waste cellulose supported CuInSnS QDs composite nanoparticles. The anhydrous ethyl ether-acetonitrile mixture is prepared by mixing anhydrous ethyl ether and acetonitrile at a volume ratio of 0.1-1:

1. The molar ratio of chloropropene to 4-alkyl pyridine is 1:1-1.

5.

3. The method of claim 1, wherein the preparation of the photocatalytic material is carried out by using the amphiphilic agricultural waste cellulose loaded CuInSnS QDs composite nanoparticles. The corn stalk pith parenchymal cellulose is prepared by the following steps. First, air-dried corn stalks are peeled, ground and sieved to obtain stalk pith powder. Then, the stalk pith powder is placed in dimethyl sulfoxide containing tert-butyl hydroperoxide with a volume concentration of 3-15%, and then reacted at 30-90℃ for 0.5-5 h. After the reaction is completed, solid-liquid separation is performed, and then the solid is washed with water. Finally, the solid is naturally air-dried to obtain the corn stalk pith parenchymal cellulose. In the reaction system, the mass volume concentration of the stalk pith powder is 5-12%.

4. The method of claim 1, wherein the preparation of the photocatalytic material is carried out by using the amphiphilic agricultural waste cellulose loaded CuInSnS QDs composite nanoparticles. The concentration of the corn stalk pith parenchymal cellulose in the tetrabutylammonium hydroxide-aminoform hydroxide aqueous solution is 0.01-0.1 g / mL. In the tetrabutylammonium hydroxide-aminoform hydroxide aqueous solution, the mass volume concentration of tetrabutylammonium hydroxide is 2.5-6.0%, and the mass volume concentration of aminoform is 8.0-25.0%. For each mole of the corn stalk pith parenchymal cellulose, 1-2.5 mol of N-allyl-4-alkyl pyridinium chloride is added.

5. The method of claim 1, wherein the preparation of the photocatalytic material is carried out by using the amphiphilic agricultural waste cellulose supported CuInSnS QDs composite nanoparticles. The mass volume ratio g:mL of the amphiphilic cellulose to N,N-dimethylacetamide is 4-10%, and the mass volume ratio g:mL of lithium chloride to N,N-dimethylacetamide is 6-10%.

6. The method of claim 1, wherein the preparation of the photocatalytic material is carried out by using the amphiphilic agricultural waste cellulose supported CuInSnS QDs composite nanoparticles. In 3+ with Cu 2+ at a molar ratio of 2.16:0.722, Sn 4+ with Cu 2+ at a molar ratio of 1.01:0.722, S 2- and Cu 2+ at a molar ratio of 3:0.

722.

7. The application of the photocatalytic material prepared by the method of preparing photocatalytic material of amphiphilic agricultural waste cellulose loaded CuInSnS QDs composite nanoparticles according to any one of claims 1-6 in photocatalytic inhibition of Trichophyton rubrum ( Trichophyton rubrum ), Trichophyton mentagrophytes ( Trichophyton mentagrophytes ).​​​​

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