阅读说明：本技术 一种应用于污水处理的SnO2-MoS2修饰石墨烯气凝胶及其制法 (SnO applied to sewage treatment2-MoS2Modified graphene aerogel and preparation method thereof ) 是由 尹若谷 余丽 张爱娟 于 2021-01-18 设计创作，主要内容包括：本发明涉及水处理技术领域,且公开了一种应用于污水处理的SnO-2-MoS-2修饰石墨烯气凝胶,以石墨烯、二乙烯三胺、N,N-亚甲基双丙烯酰胺、氯化亚锡、氟化钠、硫代乙酰胺、钼酸钠为原料,得到超支化聚酰胺胺功能化石墨烯负载MoS-2空心球修饰F掺杂SnO-2纳米花,超支化聚酰胺胺功能化石墨烯具有超高的比表面积、丰富的氨基基团和氢键以及大量的空腔结构,有利于吸附更多的甲基橙等有机染料,F掺杂促进SnO-2吸收带边红移,拓宽光吸收范围,MoS-2与SnO-2形成异质结,促进光生电子-空穴的分离,光生电子与氧气反应生成超氧负离子,空穴与水反应生成羟基自由基,具有强氧化性的超氧负离子、羟基自由基可以将甲基橙等有机染料氧化为小分子物质。(The invention relates to the technical field of water treatment and discloses SnO applied to sewage treatment 2 ‑MoS 2 Modified graphene aerogel is prepared by taking graphene, diethylenetriamine, N-methylene bisacrylamide, stannous chloride, sodium fluoride, thioacetamide and sodium molybdate as raw materials to obtain hyperbranched polyimideAmine functionalized graphene loaded MoS 2 Hollow sphere modified F-doped SnO 2 The nanoflower and hyperbranched polyamidoamine functionalized graphene has ultrahigh specific surface area, abundant amino groups and hydrogen bonds and a large number of cavity structures, is favorable for adsorbing more organic dyes such as methyl orange and the like, and promotes SnO by doping F 2 Red shift of absorption band edge, broadening light absorption range, MoS 2 With SnO 2 The organic dye such as methyl orange and the like can be oxidized into small molecular substances by the superoxide anion and the hydroxyl radical with strong oxidizing property.)

1. SnO applied to sewage treatment₂-MoS₂Modified graphene aerogel, its characterized in that: SnO applied to sewage treatment₂-MoS₂The preparation method of the modified graphene aerogel comprises the following steps:

(1) carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a methanol solvent, performing ultrasonic dispersion uniformly, reacting, removing the solvent by rotary evaporation, washing and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding sodium hydroxide into a deionized water solvent, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant of cetyl trimethyl ammonium bromide, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction, cooling, performing centrifugal separation, washing and drying to obtain fluorine-doped stannic oxide nanoflowers;

(4) adding thioacetamide, sodium molybdate and fluorine-doped tin oxide nanoflower into a deionized water solvent, performing uniform ultrasonic dispersion, performing hydrolysis reaction, adding ethanol to promote dispersion, precipitating a product with dilute hydrochloric acid, performing centrifugal separation, washing and drying, placing the dried product into a tubular furnace, calcining, and cooling to obtain molybdenum disulfide hollow sphere modified fluorine-doped tin oxide nanoflower;

(5) adding molybdenum disulfide hollow spheres to a deionized water solvent to modify fluorine-doped stannic oxide nanoflower and hyperbranched polyamidoamine functionalized graphene, uniformly dispersing by ultrasonic waves, placing the mixture in a reaction kettle, carrying out hydrothermal reaction, and freeze-drying to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

2. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: in the step (2), the mass ratio of diethylenetriamine to N, N-methylene bisacrylamide to aminated graphene is 10-20:15-30: 10.

3. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: the reaction condition in the step (2) is that the reflux reaction is carried out for 6-9h at the temperature of 45-60 ℃.

4. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: the mass ratio of the sodium hydroxide, the stannous chloride, the sodium fluoride and the hexadecyl trimethyl ammonium bromide in the step (3) is 60-120:100:0.9-1.5: 120-.

5. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: the hydrothermal reaction condition in the step (3) is hydrothermal reaction at 140-200 ℃ for 24-32 h.

6. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: thioacetyl sulfide in the step (4)The mass ratio of the amine to the sodium molybdate to the fluorine-doped stannic oxide nanoflower is 40-70:15-30: 100.

7. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: the hydrolysis reaction in the step (4) is carried out for 6-12min at 85-100 ℃.

8. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: the calcination condition in the step (4) is calcination for 0.5-2h at the temperature of 700-800 ℃ in a hydrogen atmosphere.

9. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: the mass ratio of the molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower to the hyperbranched polyamidoamine functionalized graphene in the step (5) is 3-6: 10.

10. SnO applied to sewage treatment according to claim 1₂-MoS₂Modified graphene aerogel, its characterized in that: the hydrothermal reaction condition in the step (5) is that the hydrothermal reaction is carried out for 8-15h at the temperature of 160-200 ℃.

Technical Field

The invention relates to the technical field of water treatment, in particular to SnO applied to sewage treatment₂-MoS₂Modified graphene aerogel and a preparation method thereof.

Background

At present, the variety of dyes all over 10 million, the yield per year exceeds 700 million tons, and the increase is still ongoing, in the process of producing dyes, the loss of dyes and the discharge of printing and dyeing wastewater are often accompanied with the outflow of partial dyes, and in the process of printing and dyeing, the loss of dyes and the discharge of printing and dyeing wastewater can also occur, which causes serious environmental pollution, especially acid azo dyes with stable chemical structure, strong oxidation resistance, and difficult degradation, such as methyl orange, and the like, if the acid azo dyes are not treated and directly discharged, the ecological system can be seriously damaged, and further the health of human beings can be harmed The photocatalytic degradation method can decompose organic dyes such as methyl orange and the like into small molecular substances such as water, carbon dioxide and the like which are harmless to the environment, and therefore, the photocatalytic degradation method is widely applied to the field of water treatment.

The efficiency of the photocatalytic degradation method mainly depends on the selection of the photocatalyst, and the prior semiconductor photocatalytic materials ZnO and TiO₂、WO₃、SnO₂The like have excellent photocatalytic performance and are widely applied to the fields of photocatalytic hydrogen production and degradation, wherein n-type semiconductor SnO₂Has the advantages of wider forbidden band width, lower toxicity, better chemical stability, lower cost, excellent photocatalytic activity and the like, and is applied to the fields of gas sensitivity, lithium ion batteries, photocatalysis and the likeBut the method is widely applied, but the photoproduction electron-hole is easy to recombine, the sunlight utilization rate is low, the application range is greatly limited, the modification treatment is needed to be carried out on the compound, and the doping of elements can improve SnO₂Overall performance of, and p-type semiconductor MoS₂Has narrower forbidden band width, better conductivity and excellent electrochemical and optical properties, is widely applied to the fields of lithium ion batteries, photocatalysis and the like, and is SnO₂Compounding to obviously improve SnO₂The graphene has the advantages of large specific surface area, good conductivity and the like, is widely applied to the fields of lithium ion batteries, photocatalysis, adsorption and the like, and can further improve the adsorption performance of the graphene on organic dyes such as methyl orange and the like through chemical modification.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides SnO applied to sewage treatment₂-MoS₂The modified graphene aerogel and the preparation method thereof solve the problem of SnO₂The photo-generated electrons and holes of the photocatalyst are easy to recombine, the sunlight utilization rate is low, and the adsorption performance is poor.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: SnO applied to sewage treatment₂-MoS₂Modified graphene aerogel, and SnO applied to sewage treatment₂-MoS₂The preparation method of the modified graphene aerogel comprises the following steps:

(1) carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding methanol solvent, diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a three-necked bottle, performing uniform ultrasonic dispersion, performing reaction, removing the solvent by rotary evaporation, washing with acetone, and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding a deionized water solvent and sodium hydroxide into a three-mouth bottle, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant cetyl trimethyl ammonium bromide, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction, cooling to room temperature, performing centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying to obtain fluorine-doped stannic oxide nanoflowers;

(4) adding a deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped tin oxide nanoflowers into a three-neck flask, ultrasonically dispersing uniformly, performing hydrolysis reaction, adding ethanol to promote dispersion, precipitating a product with dilute hydrochloric acid, performing centrifugal separation, washing with deionized water, drying, placing the dried product into a tubular furnace, calcining, and cooling to room temperature to obtain molybdenum disulfide hollow sphere modified fluorine-doped tin oxide nanoflowers;

(5) adding a deionized water solvent, molybdenum disulfide hollow spheres modified fluorine-doped stannic oxide nanoflower and hyperbranched polyamidoamine functionalized graphene into a three-necked flask, ultrasonically dispersing uniformly, placing the three-necked flask in a reaction kettle, carrying out hydrothermal reaction, and freeze-drying to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

Preferably, the mass ratio of diethylenetriamine, N-methylene bisacrylamide and aminated graphene in the step (2) is 10-20:15-30: 10.

Preferably, the reaction condition in the step (2) is reflux reaction at 45-60 ℃ for 6-9 h.

Preferably, the mass ratio of the sodium hydroxide, the stannous chloride, the sodium fluoride and the hexadecyl trimethyl ammonium bromide in the step (3) is 60-120:100:0.9-1.5: 120-.

Preferably, the conditions of the hydrothermal reaction in the step (3) are that the hydrothermal reaction is carried out for 24-32h at 140-200 ℃.

Preferably, the mass ratio of the thioacetamide, the sodium molybdate and the fluorine-doped stannic oxide nanoflower in the step (4) is 40-70:15-30: 100.

Preferably, the hydrolysis reaction in the step (4) is carried out at 85-100 ℃ for 6-12 min.

Preferably, the calcination condition in the step (4) is calcination in a hydrogen atmosphere at 700-800 ℃ for 0.5-2 h.

Preferably, the mass ratio of the molybdenum disulfide hollow sphere modified fluorine doped stannic oxide nanoflower to the hyperbranched polyamidoamine functionalized graphene in the step (5) is 3-6: 10.

Preferably, the conditions of the hydrothermal reaction in the step (5) are that the hydrothermal reaction is carried out for 8-15h at the temperature of 160-200 ℃.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

SnO applied to sewage treatment₂-MoS₂The modified graphene aerogel takes aminated graphene as a central point, amino and imino on aminated graphene and diethylenetriamine and double bonds on N, N-methylene-bisacrylamide undergo a Michelal addition reaction to obtain hyperbranched polyamidoamine functionalized graphene, and Sn is reacted in an alkaline environment²⁺Rapid hydrolysis to Sn (OH)₂Further oxidized to form Sn (OH)₄Further with OH^-Reaction to form Sn (OH)₆ ^2-Hydrothermal reaction to produce SnO₂Nanocrystalline is coagulated and nucleated, and further directionally grows to form SnO along the direction of acting force with reduced surface energy under the action of cetyl trimethyl ammonium bromide serving as a surfactant₂The nanosheets further randomly growing in other directions to form SnO₂Nanometer flower and sodium fluoride as doping source to obtain F-doped SnO₂Nano flower, SnO₂Unique nano flower-like shape, super-high specific surface area, benefit to expose photocatalytic degradation active site, and using it as substrate, hydrochloric acid and high-temp. accelerating hydrolysis of thioacetamide to produce H₂S, further reacting with sodium molybdate to dope SnO in F₂In-situ growth of MoS on nanoflower_xSeed crystals further in MoS_xPrecipitation of MoS on seed crystals_xGenerating MoS_xSpherical nanoparticles, calcined, MoS_xGenerating MoS₂And H₂Obtaining MoS₂Hollow sphere modified F-doped SnO₂Nanoflower, MoS₂Unique hollow spherical shape, and has ultrahigh specific surface area, thereby being beneficial to exposing more photocatalytic degradationActive sites, hyperbranched polyamidoamine functionalized graphene as a carrier, and MoS₂Hollow sphere modified F-doped SnO₂The nano flower is used as an active substance to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

SnO applied to sewage treatment₂-MoS₂The modified graphene aerogel and the hyperbranched polyamidoamine functionalized graphene have ultrahigh specific surface area, so that more adsorption active sites can be exposed, the molecular structure of the hyperbranched polyamidoamine contains abundant amino groups and hydrogen bonds, more adsorption active sites can be further exposed, and abundant amino groups are protonated in a weak acid environment, so that the hyperbranched polyamidoamine has more positive charges, the electrostatic attraction with organic dyes such as methyl orange with negative charges is increased, the hyperbranched polyamidoamine has excellent hydrophilicity, a large number of cavity structures are formed in the process of forming the hyperbranched polyamidoamine through Michelal addition reaction, and the hyperbranched polyamidoamine and the graphene have synergistic effect, so that the hyperbranched polyamidoamine is beneficial to adsorbing more organic dyes such as methyl orange.

SnO applied to sewage treatment₂-MoS₂Modifying graphene aerogel, doping F atoms into SnO₂In the crystal lattice of (2), promoting SnO₂Nanocrystalline growth to SnO₂Further increase the specific surface area of the catalyst and simultaneously enable SnO₂The absorption band edge red shift widens SnO₂Absorption of light in the range of SnO₂Utilization ratio of sunlight, p-type semiconductor MoS₂With n-type semiconductors SnO₂Forming a p-n heterojunction structure such that MoS₂And SnO₂The Fermi energy levels of the contact surfaces are the same, so that energy bands near the contact surfaces are dislocated to form an internal electric field, and under the action of the internal electric field, photoproduction electrons and holes are promoted to pass through the contact surfaces to be separated, so that SnO is enabled₂Hole transfer to MoS in the valence band₂On the price band, and MoS₂Transfer of photo-generated electrons on conduction band from SnO₂On the conduction band of the organic electroluminescent device, separation of photogenerated electrons and holes is promoted, the photogenerated electrons react with oxygen to generate superoxide anions, and the holes react with water to generate hydroxyl radicalsThe organic dye such as methyl orange can be oxidized into small molecular substance by the super-oxygen anion and the hydroxyl radical with strong oxidizing property.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: SnO applied to sewage treatment₂-MoS₂Modified graphene aerogel applied to SnO of sewage treatment₂-MoS₂The preparation method of the modified graphene aerogel comprises the following steps:

(1) carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding methanol solvent, diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a three-necked bottle, wherein the mass ratio of the methanol solvent to the diethylenetriamine to the N, N-methylene bisacrylamide to the aminated graphene is 10-20:15-30:10, performing ultrasonic dispersion uniformly, performing reflux reaction at 45-60 ℃ for 6-9h, removing the solvent by rotary evaporation, washing with acetone, and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding a deionized water solvent and sodium hydroxide into a three-mouth bottle, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant of cetyl trimethyl ammonium bromide, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction at the temperature of 140-200 ℃ for 24-32h, cooling to room temperature, performing centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying to obtain fluorine-doped stannic oxide nanoflower, wherein the mass ratio of the sodium hydroxide to the stannous chloride to the sodium fluoride to the surfactant of cetyl trimethyl ammonium bromide is 60-120:100:0.9-1.5: 120;

(4) adding a deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped stannic oxide nanoflower into a three-neck flask, wherein the mass ratio of the deionized water solvent to the thioacetamide to the sodium molybdate to the fluorine-doped stannic oxide nanoflower is 40-70:15-30:100, performing ultrasonic dispersion uniformly, performing hydrolysis reaction at 85-100 ℃ for 6-12min, adding ethanol to promote dispersion, precipitating a product by using dilute hydrochloric acid, performing centrifugal separation, washing and drying by using deionized water, placing the dried product into a tubular furnace, calcining for 0.5-2h at 800 ℃ in a hydrogen atmosphere, and cooling to room temperature to obtain molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower;

(5) to threeAdding deionized water solvent, molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower and hyperbranched polyamidoamine functionalized graphene into a mouth bottle, wherein the mass ratio of the deionized water solvent to the molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower to the hyperbranched polyamidoamine functionalized graphene is 3-6:10, uniformly dispersing by ultrasonic, placing the mouth bottle in a reaction kettle, carrying out hydrothermal reaction for 8-15h at the temperature of 160-200 ℃, and carrying out freeze drying to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

Example 1

(1) Carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding methanol solvent, diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a three-necked bottle, wherein the mass ratio of the methanol solvent to the diethylenetriamine to the N, N-methylene bisacrylamide to the aminated graphene is 10:15:10, performing ultrasonic dispersion uniformly, performing reflux reaction for 6 hours at 45 ℃, removing the solvent by rotary evaporation, washing with acetone, and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding a deionized water solvent and sodium hydroxide into a three-neck flask, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant of cetyl trimethyl ammonium bromide, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction at 140 ℃ for 24 hours, cooling to room temperature, performing centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying to obtain fluorine-doped stannic oxide nanoflowers;

(4) adding a deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped stannic oxide nanoflower into a three-neck flask in a mass ratio of 40:15:100, uniformly dispersing by ultrasonic, carrying out hydrolysis reaction at 85 ℃ for 6min, adding ethanol to promote dispersion, precipitating a product by using dilute hydrochloric acid, carrying out centrifugal separation, washing the product by using deionized water, drying the product, placing the dried product in a tubular furnace, calcining the product at 700 ℃ in a hydrogen atmosphere for 0.5h, and cooling the product to room temperature to obtain molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower;

(5) adding deionized water solvent, molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower and hyperbranched polyamide amine functionalized into a three-neck flaskGraphene with the mass ratio of 3:10, uniformly dispersing by ultrasonic, placing the graphene in a reaction kettle, carrying out hydrothermal reaction for 8 hours at 160 ℃, and carrying out freeze drying to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

Example 2

(1) Carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding methanol solvent, diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a three-necked bottle, wherein the mass ratio of the methanol solvent to the diethylenetriamine to the N, N-methylene bisacrylamide to the aminated graphene is 13.5:20:10, performing ultrasonic dispersion uniformly, performing reflux reaction at 50 ℃ for 7 hours, performing rotary evaporation to remove the solvent, washing with acetone, and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding a deionized water solvent and sodium hydroxide into a three-neck flask, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant of cetyl trimethyl ammonium bromide, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction at 160 ℃ for 27 hours, cooling to room temperature, performing centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying to obtain fluorine-doped stannic oxide nanoflowers;

(4) adding a deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped stannic oxide nanoflower into a three-necked bottle, wherein the mass ratio of the deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped stannic oxide nanoflower is 50:20:100, performing ultrasonic dispersion uniformly, performing hydrolysis reaction for 8min at 90 ℃, adding ethanol to promote dispersion, precipitating a product with dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water, drying the product, placing the dried product into a tubular furnace, calcining the product for 1h at 735 ℃ in a hydrogen atmosphere, and cooling the product to room temperature to obtain molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower;

(5) adding deionized water solvent, molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower and hyperbranched polyamidoamine functionalized graphene into a three-necked flask, wherein the mass ratio of the deionized water solvent to the molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower to the hyperbranched polyamidoamine functionalized graphene is 4:10, uniformly dispersing by ultrasonic, placing the mixture into a reaction kettle, carrying out hydrothermal reaction at 170 ℃ for 10.5h, and freeze-drying to obtain the modified fluorine-doped stannic oxide nanoflowerTo SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

Example 3

(1) Carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding methanol solvent, diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a three-necked bottle, wherein the mass ratio of the methanol solvent to the diethylenetriamine to the N, N-methylene bisacrylamide to the aminated graphene is 17:25:10, performing ultrasonic dispersion uniformly, performing reflux reaction at 55 ℃ for 8 hours, removing the solvent by rotary evaporation, washing with acetone, and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding a deionized water solvent and sodium hydroxide into a three-neck flask, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant of cetyl trimethyl ammonium bromide, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction at 180 ℃ for 30 hours, cooling to room temperature, performing centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying to obtain fluorine-doped stannic oxide nanoflowers;

(4) adding a deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped stannic oxide nanoflower into a three-neck flask in a mass ratio of 60:25:100, uniformly dispersing by ultrasonic, carrying out hydrolysis reaction at 95 ℃ for 10min, adding ethanol to promote dispersion, precipitating a product by using dilute hydrochloric acid, carrying out centrifugal separation, washing the product by using deionized water, drying the product, placing the dried product in a tubular furnace, calcining the product at 770 ℃ in a hydrogen atmosphere for 1.5h, and cooling the product to room temperature to obtain molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower;

(5) adding deionized water solvent, molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower and hyperbranched polyamidoamine functionalized graphene into a three-neck flask, wherein the mass ratio of the deionized water solvent to the molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower to the hyperbranched polyamidoamine functionalized graphene is 5:10, ultrasonically dispersing uniformly, placing the mixture into a reaction kettle, carrying out hydrothermal reaction for 13 hours at 185 ℃, and carrying out freeze drying to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

Example 4

(1) Carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding methanol solvent, diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a three-necked bottle, wherein the mass ratio of the methanol solvent to the diethylenetriamine to the N, N-methylene bisacrylamide to the aminated graphene is 20:30:10, performing ultrasonic dispersion uniformly, performing reflux reaction at 60 ℃ for 9 hours, removing the solvent by rotary evaporation, washing with acetone, and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding a deionized water solvent and sodium hydroxide into a three-neck flask, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant of cetyl trimethyl ammonium bromide, wherein the mass ratio of the sodium hydroxide to the stannous chloride to the sodium fluoride to the cetyl trimethyl ammonium bromide is 120:100:1.5:200, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction at 200 ℃ for 32 hours, cooling to room temperature, performing centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying to obtain fluorine-doped stannic oxide nanoflowers;

(4) adding a deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped stannic oxide nanoflower into a three-neck flask, wherein the mass ratio of the deionized water solvent to the thioacetamide to the sodium molybdate to the fluorine-doped stannic oxide nanoflower is 70:30:100, performing ultrasonic dispersion uniformly, performing hydrolysis reaction at 100 ℃ for 12min, adding ethanol to promote dispersion, precipitating a product with dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water, drying the product, placing the dried product in a tubular furnace, calcining the product at 800 ℃ in a hydrogen atmosphere for 2h, and cooling the product to room temperature to obtain molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower;

(5) adding deionized water solvent, molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower and hyperbranched polyamidoamine functionalized graphene into a three-neck flask, wherein the mass ratio of the deionized water solvent to the molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower to the hyperbranched polyamidoamine functionalized graphene is 6:10, ultrasonically dispersing uniformly, placing the mixture into a reaction kettle, carrying out hydrothermal reaction for 15 hours at 200 ℃, and carrying out freeze drying to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

Comparative example 1

(1) Carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding methanol solvent, diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a three-necked bottle, wherein the mass ratio of the methanol solvent to the diethylenetriamine to the N, N-methylene bisacrylamide to the aminated graphene is 8:12:10, performing ultrasonic dispersion uniformly, performing reflux reaction at 45 ℃ for 6 hours, removing the solvent by rotary evaporation, washing with acetone, and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding a deionized water solvent and sodium hydroxide into a three-neck flask, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant of cetyl trimethyl ammonium bromide, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction at 140 ℃ for 24 hours, cooling to room temperature, performing centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying to obtain fluorine-doped stannic oxide nanoflowers, wherein the mass ratio of the sodium hydroxide to the stannous chloride to the sodium fluoride to obtain a surfactant of cetyl trimethyl ammonium bromide is 48:100:0.72: 96;

(4) adding a deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped stannic oxide nanoflower into a three-neck flask, wherein the mass ratio of the deionized water solvent to the thioacetamide to the sodium molybdate to the fluorine-doped stannic oxide nanoflower is 32:12:100, performing ultrasonic dispersion uniformly, performing hydrolysis reaction at 85 ℃ for 6min, adding ethanol to promote dispersion, precipitating a product with dilute hydrochloric acid, performing centrifugal separation, washing the product with deionized water, drying the product, placing the dried product in a tube furnace, calcining the product at 700 ℃ in a hydrogen atmosphere for 0.5h, and cooling the product to room temperature to obtain molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower;

(5) adding deionized water solvent, molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower and hyperbranched polyamidoamine functionalized graphene into a three-neck flask, wherein the mass ratio of the deionized water solvent to the molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower to the hyperbranched polyamidoamine functionalized graphene is 2.4:10, uniformly dispersing the two by ultrasonic, placing the mixture into a reaction kettle, carrying out hydrothermal reaction at 160 ℃ for 8 hours, and carrying out freeze drying to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

Comparative example 2

(1) Carrying out amination modification on graphene by using diethylenetriamine to obtain aminated graphene;

(2) adding methanol solvent, diethylenetriamine, N-methylene bisacrylamide and aminated graphene into a three-necked bottle, wherein the mass ratio of the methanol solvent to the diethylenetriamine to the N, N-methylene bisacrylamide to the aminated graphene is 24:36:10, performing ultrasonic dispersion uniformly, performing reflux reaction at 60 ℃ for 9 hours, removing the solvent by rotary evaporation, washing with acetone, and drying to obtain hyperbranched polyamidoamine functionalized graphene;

(3) adding a deionized water solvent and sodium hydroxide into a three-neck flask, uniformly dispersing by ultrasonic treatment, dropwise adding a stannous chloride aqueous solution while performing ultrasonic treatment, adding sodium fluoride and a surfactant of cetyl trimethyl ammonium bromide, wherein the mass ratio of the sodium hydroxide to the stannous chloride to the sodium fluoride to the cetyl trimethyl ammonium bromide is 144:100:1.8:240, uniformly dispersing by ultrasonic treatment, placing the mixture into a reaction kettle, performing hydrothermal reaction at 200 ℃ for 32 hours, cooling to room temperature, performing centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying to obtain fluorine-doped stannic oxide nanoflowers;

(4) adding a deionized water solvent, thioacetamide, sodium molybdate and fluorine-doped stannic oxide nanoflower into a three-neck flask in a mass ratio of 84:36:100, uniformly dispersing by ultrasonic, carrying out hydrolysis reaction at 100 ℃ for 12min, adding ethanol to promote dispersion, precipitating a product by using dilute hydrochloric acid, carrying out centrifugal separation, washing the product by using deionized water, drying the product, placing the dried product in a tubular furnace, calcining the product for 2h at 800 ℃ in a hydrogen atmosphere, and cooling the product to room temperature to obtain molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower;

(5) adding deionized water solvent, molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower and hyperbranched polyamidoamine functionalized graphene into a three-neck flask, wherein the mass ratio of the deionized water solvent to the molybdenum disulfide hollow sphere modified fluorine-doped stannic oxide nanoflower to the hyperbranched polyamidoamine functionalized graphene is 7.2:10, uniformly dispersing the two by ultrasonic, placing the mixture into a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 15 hours, and carrying out freeze drying to obtain SnO applied to sewage treatment₂-MoS₂Modifying the graphene aerogel.

10mg of SnO applied to sewage treatment and obtained in example and comparative example and applied to sewage treatment were added to 50mL of methyl orange solution with a mass concentration of 20mg/L₂-MoS₂Modifying graphene aerogel, dispersing uniformly, adjusting the pH value of the solution to 6, stirring for 90min at 25 ℃, centrifuging to remove solids to obtain a degraded solution, measuring the concentration of methyl orange in the solution by using an L5 type ultraviolet-visible spectrophotometer, and calculating the adsorption rate.

10mg of SnO applied to sewage treatment and obtained in example and comparative example and applied to sewage treatment were added to 50mL of methyl orange solution with a mass concentration of 20mg/L₂-MoS₂Modifying graphene aerogel, dispersing uniformly, adjusting the pH value of the solution to 6, irradiating for 90min by using a 500W xenon lamp, centrifuging to remove solids to obtain a degraded solution, measuring the concentration of methyl orange in the solution by using an L5 type ultraviolet-visible spectrophotometer, and calculating the degradation rate.