Copper sulfide-platinum mesh ultrathin nanosheets and their preparation method and application

Abstract

The present invention relates to copper sulfide-platinum mesh ultrathin nanosheets and their preparation method and application. The microstructure of the nanosheets is a two-dimensional mesh structure composed of copper sulfide and platinum. The present invention prepares copper sulfide-platinum ultrathin nanosheets by means of a replacement reaction, effectively regulating the mesh structure of the copper sulfide-platinum nanosheets, thereby improving their catalytic photodegradation performance. The copper sulfide-platinum mesh ultrathin nanosheets of the present invention have a porous and ultrathin structure that facilitates the provision of abundant active sites, a high specific surface area, and efficient charge transfer, thereby providing good photodegradation efficiency. The preparation steps are simple, the reactants are low in toxicity, and no hazardous chemicals are present, making the process environmentally friendly.

Description

Technical Field

[0001] The present invention belongs to the technical field of two-dimensional multi-metal hybrid nanomaterials, and specifically relates to a network-shaped copper sulfide-platinum hollow ultrathin nanosheet, a preparation method thereof, and catalytic degradation application. Background Art

[0002] Metal hybrid nanomaterials have important applications in catalysis, environmental science, biomedicine, energy, information technology, military equipment, aerospace, and other fields. For example, CN110918017A discloses a method for preparing precious metal / copper sulfide core-shell nanocrystals. The prepared precious metal / copper sulfide core-shell nanocrystals have significantly improved efficiency in degrading toxic gases such as formaldehyde compared to single-structure copper sulfide nanocrystals. CN110794017A discloses a method for preparing an electrochemical immunosensor for detecting procalcitonin using platinum nanoparticle-functionalized flower-shaped copper oxysulfide. Using platinum nanoparticle-functionalized flower-shaped copper oxysulfide as the substrate material and a phosphate buffer solution containing hydrogen peroxide as the base solution, a signal-attenuating electrochemical immunosensor is constructed using a layer-by-layer modification method of the electrochemical sensor. This improves the sensor sensitivity and detection limit, enabling rapid and efficient detection of procalcitonin. CN116019923A discloses a preparation method and application of a copper sulfide nanodrug encapsulating a tetravalent platinum prodrug. The prepared copper sulfide nanodrug carrier has good hydrophilicity, is conducive to circulation and distribution in the body, and has a good photothermal effect in the body.

[0003] The microstructure of nanomaterials has a significant impact on their performance. Two-dimensional metal hybrid nanomaterials have attracted widespread attention due to their unique characteristics such as large surface area, spatial confinement effect and tunable electronic properties. Nanomaterials composed of copper sulfide (CuS) and platinum (Pt) combine the semiconductor properties of CuS with the catalytic efficiency and metallic stability of Pt, showing unique synergistic properties, which are of great significance for enhancing catalytic activity and photoelectric performance as well as multifunctionality for environmental degradation, energy and biomedical applications. How to effectively regulate the microstructure of copper sulfide-platinum nanomaterials to improve their catalytic photodegradation performance is a technical problem that urgently needs to be solved. To this end, the present invention is proposed. Summary of the Invention

[0004] In view of the above-mentioned technical status, the present invention prepares copper sulfide-platinum ultrathin nanosheets by means of a replacement reaction, effectively regulates the network structure of the copper sulfide-platinum nanosheets, thereby improving their catalytic photodegradation performance.

[0005] Therefore, the first object of the present invention is to provide a copper sulfide-platinum network ultra-thin nanosheet having different pore structures.

[0006] The second object of the present invention is to provide a method for preparing copper sulfide-platinum network ultra-thin nanosheets.

[0007] The third object of the present invention is to provide an application of copper sulfide-platinum mesh ultrathin nanosheets in catalytic photodegradation.

[0008] The technical solution for achieving the above-mentioned invention object can be summarized as follows:

[0009] Copper sulfide-platinum network ultra-thin nanosheets, the microstructure of which is a two-dimensional network structure composed of copper sulfide and platinum.

[0010] According to the present invention, preferably, the thickness of the copper sulfide-platinum network ultra-thin nanosheets is 0.5-20 nm.

[0011] According to the present invention, preferably, in the copper sulfide-platinum network ultra-thin nanosheets, the molar ratio of copper sulfide to platinum is (5-150):1.

[0012] According to the present invention, the method for preparing the above-mentioned copper sulfide-platinum network ultra-thin nanosheets comprises the following steps:

[0013] (1) adding a sulfur source and a copper salt to an organic solvent A and mixing them uniformly, reacting them at a certain temperature for a period of time, washing them with an organic solvent B, separating and purifying them, and then dispersing them into the organic solvent A;

[0014] (2) adding platinum salt to step (1), reacting at a certain temperature for a period of time, washing with an organic solvent B, separating and purifying to obtain the final product, copper sulfide-platinum mesh ultrathin nanosheets.

[0015] According to the present invention, preferably, in step (1), the sulfur source is one of sulfur powder, glutathione, sodium thiosulfate, L-cysteine, and L-cystine, and is more preferably sulfur powder;

[0016] Preferably, the copper salt is one of copper chloride, copper bromide, copper sulfate, copper nitrate, copper acetate, and copper acetylacetonate, more preferably copper acetylacetonate;

[0017] Preferably, the organic solvent A is one of benzyl alcohol, oleylamine, bis(2-hydroxyethyl)oleylamine, oleylpropylenediamine, and oleic acid, and more preferably oleylpropylenediamine.

[0018] According to the present invention, preferably, in step (1), the molar ratio of the sulfur source to the copper salt is (0.5-20):1.

[0019] According to the present invention, preferably, in step (1), the certain temperature is in the range of 50-250°C, more preferably 100-200°C, and most preferably 150°C;

[0020] Preferably, the period of time is in the range of 0.5-10 hours, more preferably 1-2 hours, and most preferably 1 hour.

[0021] According to the present invention, preferably, in step (2), the platinum salt is one of platinous chloride, platinum acetylacetonate, platinum chloride, and chloroplatinic acid, and more preferably chloroplatinic acid;

[0022] Preferably, the organic solution B is one of cyclohexane, toluene, ethyl acetate, dichloromethane, and tetrahydrofuran, more preferably cyclohexane.

[0023] According to the present invention, preferably, in step (2), the certain temperature is in the range of 50-300°C, more preferably 100-250°C, and most preferably 220°C;

[0024] Preferably, the period of time is in the range of 0.5-10 hours, more preferably 1-2 hours, and most preferably 1 hour.

[0025] According to the present invention, preferably, the molar ratio of the copper salt in step (1) to the platinum salt in step (2) is (0.5-150):1.

[0026] According to the present invention, preferably, in steps (1) and (2), the separation and purification method is at least one of centrifugation, filtration, and decantation, and centrifugation is more preferably used.

[0027] According to the present invention, the copper sulfide-platinum network ultrathin nanosheets are used for photocatalytic degradation; preferably for photocatalytic degradation of methylene blue dye.

[0028] Beneficial effects of the present invention:

[0029] 1. The present invention has for the first time achieved effective control of the two-dimensional network structure of copper sulfide-platinum nanosheets, obtained nanosheets with different pore structures, and expanded the limitations of the material's morphological structure.

[0030] 2. The copper sulfide-platinum mesh ultrathin nanosheets prepared in the present invention can be used as a catalyst for photocatalytic degradation. Their porous structure and ultrathin structure are conducive to providing abundant active sites, high specific surface area, efficient charge transfer, etc., and can provide good photodegradation efficiency.

[0031] 3. The preparation steps of the copper sulfide-platinum mesh ultrathin nanosheets of the present invention are simple, the reactants are low-toxic, no hazardous chemicals are contained, and the process is green and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 .This is a transmission electron microscope photograph of the product prepared in Example 1 of the present invention.

[0033] Figure 2. X-ray diffraction pattern of the product prepared in Example 1 of the present invention, as well as comparison with standard PDF cards of CuS and Pt.

[0034] Figure 3 . This is the UV-visible absorption spectrum of the product prepared in Example 1 of the present invention, and its comparison with copper sulfide nanosheets.

[0035] Figure 4 . The UV-visible absorption spectrum of the solution of the product prepared in Example 1 of the present invention changes with time during the process of catalyzing the photodegradation of methylene blue dye.

[0036] Figure 5 The product prepared in Example 1 of the present invention catalyzes the photodegradation of methylene blue dye, the concentration of methylene blue at different reaction times (C t ) to the initial concentration (C0) over time.

[0037] Figure 6 The product prepared in Example 1 of the present invention catalyzes the photodegradation of methylene blue dye, ln (C t The values ​​of / C0) at different irradiation times and the fitting straight line, the apparent reaction constant is 0.311min -1 .

[0038] Figure 7 . This is the conversion rate of five cycles of photodegradation of methylene blue dye catalyzed by the product prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0039] The present invention prepares copper sulfide-platinum ultrathin nanosheets by means of a replacement reaction, effectively regulates the network structure of the copper sulfide-platinum nanosheets, thereby improving their catalytic photodegradation performance.

[0040] The copper sulfide-platinum mesh ultrathin nanosheets of the present invention are composed of a copper sulfide-platinum composite, forming a two-dimensional, ultrathin mesh. Their porous and ultrathin structure provides abundant active sites, a high specific surface area, and efficient charge transfer, resulting in excellent photodegradation efficiency.

[0041] In one or more preferred embodiments, the copper sulfide-platinum network ultra-thin nanosheets have a thickness of 0.5-20 nm.

[0042] In one or more preferred embodiments, in the copper sulfide-platinum network ultra-thin nanosheets, the molar ratio of copper sulfide to platinum is (5-150):1, for example: 20:1, 30:1, 50:1, 80:1, 100:1, 120:1.

[0043] According to the present invention, a method for preparing a copper sulfide-platinum network ultra-thin nanosheet comprises the following steps:

[0044] (1) adding a sulfur source and a copper salt to an organic solvent A and mixing them uniformly, reacting them at a certain temperature for a period of time, washing them with an organic solvent B, separating and purifying them, and then dispersing them into the organic solvent A;

[0045] (2) adding platinum salt to step (1), reacting at a certain temperature for a period of time, washing with an organic solvent B, separating and purifying to obtain the final product, copper sulfide-platinum mesh ultrathin nanosheets.

[0046] According to the present invention, step (1) is a process for preparing copper sulfide nanosheets. The thickness of the nanosheets can be controlled by adjusting the ratio of the sulfur source and the copper salt and adjusting the type of the copper salt.

[0047] In one or more preferred embodiments, the sulfur source is one of sulfur powder, glutathione, sodium thiosulfate, L-cysteine, and L-cystine, and is more preferably sulfur powder.

[0048] In one or more preferred embodiments, the copper salt is one of copper chloride, copper bromide, copper sulfate, copper nitrate, copper acetate, and copper acetylacetonate, more preferably copper acetylacetonate.

[0049] In one or more preferred embodiments, the organic solvent A is one of benzyl alcohol, oleylamine, bis(2-hydroxyethyl)oleylamine, oleylpropylenediamine, and oleic acid, and more preferably oleylpropylenediamine.

[0050] In one or more preferred embodiments, the molar ratio of the sulfur source to the copper salt in step (1) is (0.5-20):1.

[0051] In one or more preferred embodiments, the certain temperature in step (1) is in the range of 50-250°C, more preferably 100-200°C, and most preferably 150°C;

[0052] Preferably, the period of time is in the range of 0.5-10 hours, more preferably 1-2 hours, and most preferably 1 hour.

[0053] According to the present invention, step (2) is a process for preparing copper sulfide-platinum mesh nanosheets. The thickness of the thin layer can be adjusted by controlling the temperature, and the pore structure can be adjusted by changing the amount of platinum salt added.

[0054] In one or more preferred embodiments, the platinum salt is one of platinous chloride, platinum acetylacetonate, platinum chloride, and chloroplatinic acid, more preferably chloroplatinic acid;

[0055] Preferably, the organic solution B is one of cyclohexane, toluene, ethyl acetate, dichloromethane, and tetrahydrofuran, more preferably cyclohexane.

[0056] In one or more preferred embodiments, in step (2), the certain temperature is in the range of 50-300°C, more preferably 100-250°C, and most preferably 220°C;

[0057] Preferably, the period of time is in the range of 0.5-10 hours, more preferably 1-2 hours, and most preferably 1 hour.

[0058] In one or more preferred embodiments, the molar ratio of the copper salt in step (1) to the platinum salt in step (2) is (0.5-150):1.

[0059] In one or more preferred embodiments, in steps (1) and (2), the separation and purification method is at least one of centrifugation, filtration, and decantation, and centrifugation is more preferred.

[0060] According to the present invention, the copper sulfide-platinum network ultrathin nanosheets are used for photocatalytic degradation; preferably for photocatalytic degradation of methylene blue dye.

[0061] Example 1

[0062] 10 mg of copper acetylacetonate and 10 mg of sulfur powder were added to 10 mL of oleyl propylene diamine, mixed evenly, and reacted at 150°C for 1 hour. The mixture was washed with 10 mL of cyclohexane, purified by centrifugation, and redispersed in 10 mL of oleyl propylene diamine. 50 μL of a 100 mM chloroplatinic acid solution was then added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 10 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0063] Example 2

[0064] 15 mg of copper nitrate and 20 mg of sulfur powder were added to 20 mL of oleyl propylene diamine, mixed thoroughly, and reacted at 150°C for 1 hour. The mixture was washed with 15 mL of cyclohexane, purified by centrifugation, and redispersed in 20 mL of oleyl propylene diamine. 200 μL of a 50 mM chloroplatinic acid solution was added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 10 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0065] Example 3

[0066] 50 mg of copper chloride and 120 mg of sulfur powder were added to 100 mL of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 50 mL of cyclohexane, purified by centrifugation, and redispersed in 100 mL of oleyl propylene diamine. 0.5 mL of a 100 mM chloroplatinic acid solution was then added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 50 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0067] Example 4

[0068] 0.5 g of copper acetylacetonate and 0.8 g of sulfur powder were added to 500 mL of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 150 mL of cyclohexane, purified by centrifugation, and redispersed in 300 mL of oleyl propylene diamine. 1 mL of 100 mM chloroplatinic acid solution was further added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 100 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0069] Example 5

[0070] 80 mg of copper acetylacetonate and 100 mg of sulfur powder were added to 100 mL of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 50 mL of cyclohexane, purified by centrifugation, and redispersed in 80 mL of oleyl propylene diamine. 0.3 mL of a 100 mM chloroplatinic acid solution was then added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 60 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0071] Example 6

[0072] 100 mg of copper acetylacetonate and 50 mg of glutathione were added to 100 mL of oleylpropylenediamine, mixed evenly, and reacted at 150°C for 1 hour. The mixture was washed with 80 mL of cyclohexane, purified by centrifugation, and redispersed in 100 mL of oleylpropylenediamine. 50 μL of a 100 mM chloroplatinic acid solution was then added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 50 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0073] Example 7

[0074] 200 mg of copper acetylacetonate and 150 mg of sodium thiosulfate were added to 200 mL of oleylpropylenediamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. 100 mL of cyclohexane was used for washing, purified by centrifugation, and redispersed in 200 mL of oleylpropylenediamine. 1 mL of 100 mM chloroplatinic acid solution was further added, and the mixture was reacted at 220 degrees Celsius for 1 hour. 80 mL of cyclohexane was used for washing, and the mixture was purified by centrifugation to obtain the final product.

[0075] Example 8

[0076] 1g of copper acetylacetonate and 1g of sulfur powder were added to 500mL of oleylamine, mixed evenly, and reacted at 150°C for 1 hour. The mixture was washed with 500mL of cyclohexane, purified by centrifugation, and redispersed in 300mL of oleylpropylenediamine. 6mL of a 100mM chloroplatinic acid solution was then added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 300mL of cyclohexane and purified by centrifugation to obtain the final product.

[0077] Example 9

[0078] 0.5g of copper acetylacetonate and 0.5g of sulfur powder were added to 300mL of benzyl alcohol and mixed uniformly, and the mixture was reacted at 150 degrees Celsius for 1 hour. 250mL of cyclohexane was used for washing, purified by centrifugation, and redispersed in 250mL of oleyl propylene diamine. 2mL of 100mM chloroplatinic acid solution was further added, and the mixture was reacted at 220 degrees Celsius for 1 hour. 200mL of cyclohexane was used for washing, purified by centrifugation, and the final product was obtained.

[0079] Example 10

[0080] 0.6 g of copper acetylacetonate and 0.4 g of sulfur powder were added to 500 mL of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 300 mL of cyclohexane, purified by centrifugation, and redispersed in 500 mL of oleyl propylene diamine. 1 mL of 100 mM chloroplatinic acid solution was further added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 300 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0081] Example 11

[0082] 50 mg of copper acetylacetonate and 50 mg of sulfur powder were added to 50 mL of oleyl propylene diamine, mixed evenly, and reacted at 50°C for 1 hour. The mixture was washed with 30 mL of cyclohexane, purified by centrifugation, and redispersed in 60 mL of oleyl propylene diamine. 45 μL of a 100 mM chloroplatinic acid solution was added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 80 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0083] Example 12

[0084] 30 mg of copper acetylacetonate and 40 mg of sulfur powder were added to 30 mL of oleyl propylene diamine, mixed evenly, and reacted at 250°C for 1 hour. The mixture was washed with 30 mL of cyclohexane, purified by centrifugation, and redispersed in 30 mL of oleyl propylene diamine. 100 μL of a 100 mM chloroplatinic acid solution was added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 30 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0085] Example 13

[0086] 10 mg of copper acetylacetonate and 8 mg of sulfur powder were added to 10 mL of oleyl propylene diamine, mixed evenly, and reacted at 150°C for 0.5 hours. The mixture was washed with 10 mL of cyclohexane, purified by centrifugation, and redispersed in 10 mL of oleyl propylene diamine. 45 μL of a 100 mM chloroplatinic acid solution was added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 10 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0087] Example 14

[0088] 150 mg of copper acetylacetonate and 150 mg of sulfur powder were added to 200 mL of oleyl propylene diamine, mixed evenly, and reacted at 150°C for 10 hours. The mixture was washed with 80 mL of cyclohexane, purified by centrifugation, and redispersed in 150 mL of oleyl propylene diamine. 600 μL of a 100 mM chloroplatinic acid solution was then added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 100 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0089] Example 15

[0090] 250 mg of copper acetylacetonate and 400 mg of sulfur powder were added to 300 mL of oleyl propylene diamine, mixed uniformly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 150 mL of cyclohexane, purified by centrifugation, and redispersed in 200 mL of oleyl propylene diamine. 50 mg of platinum acetylacetonate was then added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 100 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0091] Example 16

[0092] 30 mg of copper acetylacetonate and 30 mg of sulfur powder were added to 30 mL of oleyl propylene diamine, mixed evenly, and reacted at 150°C for 1 hour. The mixture was washed with 20 mL of cyclohexane, purified by centrifugation, and redispersed in 30 mL of oleyl propylene diamine. 0.15 mL of 100 mM platinous chloride was then added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 20 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0093] Example 17

[0094] 800 mg of copper acetylacetonate and 500 mg of sulfur powder were added to 800 mL of oleylpropylenediamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 300 mL of cyclohexane, purified by centrifugation, and redispersed in 500 mL of oleylamine. 5 mL of a 100 mM chloroplatinic acid solution was then added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 400 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0095] Example 18

[0096] 300 mg of copper acetylacetonate and 300 mg of sulfur powder were added to 400 mL of oleylpropylenediamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 300 mL of cyclohexane, purified by centrifugation, and redispersed in 300 mL of bis(2-hydroxyethyl)oleylamine. 200 μL of 100 mM chloroplatinic acid solution was added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 200 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0097] Example 19

[0098] 40 mg of copper acetylacetonate and 80 mg of sulfur powder were added to 80 mL of oleyl propylene diamine, mixed evenly, and reacted at 150°C for 1 hour. The mixture was washed with 50 mL of toluene, purified by centrifugation, and redispersed in 40 mL of oleyl propylene diamine. 100 μL of a 100 mM chloroplatinic acid solution was added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 30 mL of toluene and purified by centrifugation to obtain the final product.

[0099] Example 20

[0100] 60 mg of copper acetylacetonate and 50 mg of sulfur powder were added to 50 mL of oleyl propylene diamine, mixed evenly, and reacted at 150°C for 1 hour. The mixture was washed with 50 mL of dichloromethane, purified by centrifugation, and redispersed in 50 mL of oleyl propylene diamine. 600 μL of a 50 mM chloroplatinic acid solution was added, and the mixture was reacted at 220°C for 1 hour. The mixture was washed with 50 mL of dichloromethane and purified by centrifugation to obtain the final product.

[0101] Example 21

[0102] 25 mg of copper acetylacetonate and 25 mg of sulfur powder were added to 25 mL of oleyl propylene diamine, mixed thoroughly, and reacted at 150°C for 1 hour. The mixture was washed with 20 mL of cyclohexane, purified by centrifugation, and redispersed in 25 mL of oleyl propylene diamine. 100 μL of a 100 mM chloroplatinic acid solution was added, and the mixture was reacted at 50°C for 1 hour. The mixture was washed with 20 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0103] Example 22

[0104] 1.2 g of copper acetylacetonate and 1.2 g of sulfur powder were added to 1 L of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 800 mL of cyclohexane, purified by centrifugation, and redispersed in 800 mL of oleyl propylene diamine. 60 mL of a 100 mM chloroplatinic acid solution was further added, and the mixture was reacted at 300 degrees Celsius for 1 hour. The mixture was washed with 800 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0105] Example 23

[0106] 100 mg of copper acetylacetonate and 100 mg of sulfur powder were added to 100 mL of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 150 mL of cyclohexane, purified by centrifugation, and redispersed in 100 mL of oleyl propylene diamine. 0.5 mL of a 100 mM chloroplatinic acid solution was then added, and the mixture was reacted at 220 degrees Celsius for 0.5 hour. The mixture was washed with 100 mL of cyclohexane, purified by centrifugation, and the final product was obtained.

[0107] Example 24

[0108] 50 mg of copper acetylacetonate and 40 mg of sulfur powder were added to 40 mL of oleyl propylene diamine, mixed evenly, and reacted at 150°C for 1 hour. The mixture was washed with 30 mL of cyclohexane, purified by centrifugation, and redispersed in 40 mL of oleyl propylene diamine. 250 μL of a 100 mM chloroplatinic acid solution was then added, and the mixture was reacted at 220°C for 10 hours. The mixture was washed with 40 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0109] Example 25

[0110] 300 mg of copper acetylacetonate and 300 mg of sulfur powder were added to 500 mL of oleylpropylenediamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 300 mL of cyclohexane, separated and purified by decantation, and redispersed in 250 mL of oleylpropylenediamine. 1 mL of a 100 mM chloroplatinic acid solution was further added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 200 mL of cyclohexane and purified by centrifugation to obtain the final product.

[0111] Example 26

[0112] 2g of copper acetylacetonate and 2g of sulfur powder were added to 2L of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. 1.5L of cyclohexane was used for washing, the mixture was separated and purified by filtration, and redispersed in 1L of oleyl propylene diamine. 10mL of 100mM chloroplatinic acid solution was further added, and the mixture was reacted at 220 degrees Celsius for 1 hour. 1L of cyclohexane was used for washing, the mixture was purified by centrifugation, and the final product was obtained.

[0113] Example 27

[0114] 800 mg of copper acetylacetonate and 800 mg of sulfur powder were added to 800 mL of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 1 hour. The mixture was washed with 500 mL of cyclohexane, purified by centrifugation, and redispersed in 600 mL of oleyl propylene diamine. 5 mL of a 100 mM chloroplatinic acid solution was further added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 1 L of cyclohexane, separated and purified by decantation, and the final product was obtained.

[0115] Example 28

[0116] 1g of copper acetylacetonate and 1g of sulfur powder were added to 1L of oleyl propylene diamine, mixed evenly, and reacted at 150 degrees Celsius for 10 hours. The mixture was washed with 800mL of cyclohexane, purified by centrifugation, and redispersed in 1L of oleyl propylene diamine. 5mL of a 100mM chloroplatinic acid solution was further added, and the mixture was reacted at 220 degrees Celsius for 1 hour. The mixture was washed with 1L of cyclohexane, separated and purified by filtration, and the final product was obtained.

[0117] Test Example 1

[0118] Test Example: Transmission electron microscope photo of the final product prepared, such as Figure 1 As shown. Figure 1 It can be seen that the copper sulfide-platinum mesh ultrathin nanosheets present a mesh structure.

[0119] Test Example 2

[0120] Test Example: The X-ray diffraction spectrum of the final product, copper sulfide-platinum network ultra-thin nanosheets, is as follows: Figure 2 As shown. Figure 2 It can be seen that by comparing with the standard PDF cards of platinum and copper sulfide, the main component of the ultra-thin nanosheet crystals is copper sulfide structure, and the diffraction peak signal of metal Pt is weak due to its low content.

[0121] Test Example 3

[0122] Test Example: The UV-visible absorption spectra of the final product copper sulfide-platinum mesh ultrathin nanosheets and the comparison sample solid copper sulfide nanosheets are as follows: Figure 3 As shown. Figure 3 It can be seen that the copper sulfide-platinum network ultrathin nanosheet cyclohexane suspension has strong absorption in the visible light region.

[0123] Test Example 4

[0124] Test Example: Testing the application performance of the final product, copper sulfide-platinum network ultrathin nanosheets, in photocatalytic degradation of methylene blue dye, such as Figure 4 , as shown in 5, 6, and 7.

[0125] In the methylene blue photodegradation process, three solutions were first prepared: copper sulfide-platinum nanosheet solution (1 mg mL -1 ), methylene blue solution (50 mg·L -1 ) and H2O2 solution (concentration of 3.32×10 -2 mol·L -1 These solutions were mixed at a molar ratio of 1:1:40 to obtain 20 mL of an aqueous solution.

[0126] A 300W xenon lamp was used to irradiate the mixed solution of copper sulfide-platinum mesh ultrathin nanosheets, methylene blue and hydrogen peroxide, and the reaction was stirred at 6°C. Figure 4 It can be seen that as the light source irradiation time increases, the absorbance of the solution gradually decreases. Figure 5 It can be seen that the ratio of the concentration of methylene blue at different reaction times to the initial concentration decreases as the reaction time increases. Figure 6It can be seen that the apparent reaction constant for the degradation of methylene blue under the catalysis of copper sulfide-platinum mesh ultrathin nanosheets is 0.311min -1 .Depend on Figure 7 It can be seen that after five cycles of use, the conversion rate of copper sulfide-platinum mesh ultrathin nanosheets catalyzing the photodegradation of methylene blue dye did not decrease compared with the initial reaction.

Claims

1. Copper sulfide-platinum mesh ultrathin nanosheets, characterized in that: The microstructure of the nanosheet is a two-dimensional network structure composed of copper sulfide and platinum. The thickness of the copper sulfide-platinum network ultra-thin nanosheet is 0.5-20 nm, and the molar ratio of copper sulfide to platinum in the copper sulfide-platinum network ultra-thin nanosheet is (5-150):

1. The copper sulfide-platinum mesh ultra-thin nanosheets are prepared according to the following steps: (1) Add the sulfur source and copper salt to organic solvent A and mix them evenly. React them at 50-250°C for 0.5-10 hours. Wash them with organic solvent B, separate and purify them, and then disperse them into organic solvent A. The sulfur source is one of sulfur powder, glutathione, sodium thiosulfate, L-cysteine, and L-cystine; the copper salt is one of copper chloride, copper bromide, copper sulfate, copper nitrate, copper acetate, and copper acetylacetonate; the organic solvent A is oleylpropylenediamine; and the molar ratio of the sulfur source to the copper salt is (0.5-20):1; (2) Adding platinum salt to step (1), reacting at a temperature of 50-300° C. for 0.5-10 hours, washing with an organic solvent B, separating and purifying to obtain the final product, copper sulfide-platinum mesh ultrathin nanosheets; The platinum salt is one of platinous chloride, platinum acetylacetonate, platinum chloride, and chloroplatinic acid, and the molar ratio of the copper salt in step (1) to the platinum salt in step (2) is (0.5-150):

1.

2. The method for preparing the copper sulfide-platinum network ultra-thin nanosheets according to claim 1, comprising the following steps: (1) Add the sulfur source and copper salt to organic solvent A and mix them evenly. React them at 50-250°C for 0.5-10 hours. Wash them with organic solvent B, separate and purify them, and then disperse them into organic solvent A. The sulfur source is one of sulfur powder, glutathione, sodium thiosulfate, L-cysteine, and L-cystine; the copper salt is one of copper chloride, copper bromide, copper sulfate, copper nitrate, copper acetate, and copper acetylacetonate; the organic solvent A is oleylpropylenediamine; and the molar ratio of the sulfur source to the copper salt is (0.5-20):1; (2) Adding platinum salt to step (1), reacting at a temperature of 50-300°C for 0.5-10 hours, washing with an organic solvent B, separating and purifying to obtain the final product, copper sulfide-platinum mesh ultrathin nanosheets; The platinum salt is one of platinous chloride, platinum acetylacetonate, platinum chloride, and chloroplatinic acid, and the molar ratio of the copper salt in step (1) to the platinum salt in step (2) is (0.5-150):

1.

3. The method for preparing the copper sulfide-platinum network ultra-thin nanosheet according to claim 2, characterized in that: In step (2), the organic solvent B is one of cyclohexane, toluene, ethyl acetate, dichloromethane, and tetrahydrofuran.

4. The use of the copper sulfide-platinum network ultra-thin nanosheet according to claim 1, characterized in that: Used for photocatalytic degradation.

5. The use of the copper sulfide-platinum network ultra-thin nanosheet according to claim 4, characterized in that: Used for photocatalytic degradation of methylene blue dye.

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