Preparation method of silver monatomic modified sulfur indium copper and mercapto functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide by self-oxygen supply

Abstract

The application discloses a preparation method and application of a silver monatomic modified sulfur indium copper and thiol functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide by self oxygen supply, and relates to the technical field of photocatalysts. The method comprises the following steps: 1, preparing sulfur indium copper nanoparticles; 2, preparing silver monatomic modified sulfur indium copper nanoparticles; 3, preparing thiol functionalized perylene diimide; and 4, preparing silver monatomic modified sulfur indium copper and thiol functionalized perylene diimide heterojunction nanomaterials. The silver monatomic modified sulfur indium copper and thiol functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide by self oxygen supply can solve the problems of low photo-generated carrier separation efficiency, insufficient oxygen capture and activation capacity, low hydrogen peroxide production efficiency under anoxic conditions and limited copper ion release of the existing copper-based photocatalyst.

Description

Technical Field

[0001] This invention relates to the technical field of photocatalysts, specifically to the preparation and application of a heterojunction photocatalyst consisting of silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide that produces hydrogen peroxide through self-oxygen supply. Background Technology

[0002] Copper death is a novel copper-dependent cell death mechanism with significant potential applications in cancer treatment. Enhancing the release and accumulation of copper ions within tumor cells can help induce copper death and improve anti-tumor effects. However, the low oxygen content and limited reactive oxygen species levels in the tumor microenvironment restrict the sustained release of copper ions from copper-based materials, leading to insufficient therapeutic efficacy of copper death.

[0003] Hydrogen peroxide is an important reactive oxygen species molecule that can promote the release of metal ions and regulate the tumor redox microenvironment, thus playing a crucial role in enhancing copper apoptosis therapy. However, the concentration of endogenous hydrogen peroxide in tumors is low, and the hypoxic environment further limits the generation of oxygen-dependent reactive oxygen species. Therefore, developing a photocatalytic nanomaterial capable of continuously generating hydrogen peroxide in hypoxic tumors is of great significance for improving the efficacy of copper apoptosis therapy.

[0004] Indium copper sulfide (ICP-C) is a copper-based semiconductor material with a wide photoresponse range. Due to its copper content, ICP-C can serve not only as a photocatalytic component but also as a copper ion source for copper death-related applications. However, single ICP-C materials still have certain limitations, such as easy recombination of photogenerated electrons and holes, limited oxygen adsorption and activation capabilities, insufficient selectivity in the oxygen reduction reaction, and limited hydrogen peroxide generation capacity under hypoxic conditions. These issues restrict the further application of ICP-C materials in photocatalytic enhancement of copper ion release and copper death enhancement. Therefore, it is necessary to construct a novel heterojunction nanomaterial that combines self-oxygen supply capability, highly efficient photocatalytic hydrogen peroxide production capability, and the potential for enhanced copper ion release.

[0005] Therefore, developing a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst that produces hydrogen peroxide through self-oxygen supply, thereby enabling it to simultaneously possess broad spectral response, interfacial charge transfer, self-oxygen supply, and high-efficiency hydrogen peroxide production capabilities, is of great significance for addressing the insufficient photocatalytic hydrogen peroxide production under hypoxic conditions, promoting copper ion release, and enhancing copper death-related effects.

[0006] The information disclosed in this background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0007] The purpose of this invention is to provide a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide through self-oxygen supply, in order to solve the problems of insufficient hydrogen peroxide production capacity, limited copper ion release, and unsatisfactory copper death enhancement effect of existing copper-based photocatalytic materials under hypoxic conditions.

[0008] This invention utilizes silver single-atom-modified copper indium sulfide nanoparticles and combines them with thiol-functionalized perylene diimide to construct a heterojunction photocatalyst with self-oxygen-supplying hydrogen peroxide production capability. This is achieved through the following steps:

[0009] I. Preparation of copper indium sulfide nanoparticles:

[0010] Cuprous iodide and indium acetate were added to a mixed solvent of 1-octadecene and oleic acid and stirred to disperse, resulting in a uniform dispersion system. Subsequently, 1-dodecylthiol was added as a sulfur source and coordinating ligand, and the mixture was stirred and mixed again. The mixture was placed in a three-necked flask and heated under a nitrogen atmosphere to remove residual oxygen and moisture. After degassing, the reaction system was heated to the reaction temperature and maintained. After the reaction was completed, the mixture was naturally cooled to room temperature, and the product was repeatedly precipitated and washed with chloroform and ethanol. After drying, copper indium sulfide nanoparticles were obtained.

[0011] II. Preparation of silver single-atom modified copper indium sulfide nanoparticles:

[0012] Silver acetate and tributylphosphine were added to 1-octadecene and mixed thoroughly to form a silver precursor solution. After the reaction system of copper indium sulfide nanoparticles in step one cooled down, the silver precursor solution was rapidly injected into the reaction system and the reaction continued. After the reaction was completed, the product was collected by centrifugation, washed with a mixed solvent of chloroform and ethanol, and then dried to obtain silver single-atom modified copper indium sulfide nanoparticles.

[0013] III. Preparation of thiol-functionalized perylene diimide:

[0014] 3,4,9,10-perylenetetracarboxylic dianhydride, imidazole, anhydrous zinc acetate, and 2-aminoethanethiol were mixed and reacted under an inert atmosphere. After the reaction was completed, ethanol and hydrochloric acid solution were added to the system to precipitate the product, which was then acidified to obtain a crude product. The crude product was repeatedly washed with ultrapure water until neutral and dried. Subsequently, the crude product was dispersed in water, and triethylamine was added to dissolve it completely to form a homogeneous solution. Hydrochloric acid solution was then added to induce molecular reassembly. The precipitate was collected, washed with water until neutral, and dried to obtain thiol-functionalized perylene diimide.

[0015] IV. Preparation of a heterojunction photocatalyst modified with silver single atoms and indium copper sulfide and thiol-functionalized perylene diimide:

[0016] The silver-modified copper sulfide nanoparticles obtained in step two and the thiol-functionalized perylene diimide obtained in step three were dispersed separately in a solvent and uniformly dispersed by ultrasonication or stirring. The two dispersions were then mixed to ensure sufficient contact between the silver-modified copper sulfide nanoparticles and the thiol-functionalized perylene diimide. Through solvent exchange, self-assembly, or stirring, the silver-modified copper sulfide nanoparticles were uniformly loaded onto the surface of the thiol-functionalized perylene diimide, forming a tightly contacted heterojunction interface. After the reaction was complete, the product was collected by centrifugation and washed with a suitable solvent to remove unbound components. The resulting product was dried to obtain a silver-modified copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst with the ability to produce hydrogen peroxide through self-oxygenation.

[0017] The present invention also provides the silver single-atom modified copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst as a photocatalyst for photocatalytic oxygen production and photocatalytic hydrogen peroxide production, or for photocatalytic enhancement of copper ion release, or for preparation of copper death-enhancing materials.

[0018] Compared with the prior art, the silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst of the present invention, which generates hydrogen peroxide through self-oxygen supply, has the following advantages:

[0019] I. The silver single-atom modified copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst constructed in this invention has the ability to generate hydrogen peroxide by self-supplying oxygen, which can alleviate the problem of insufficient hydrogen peroxide generation under hypoxic conditions.

[0020] Second, silver single-atom sites can promote oxygen capture and activation, which is beneficial to improving the efficiency of oxygen reduction reaction and the ability to generate hydrogen peroxide.

[0021] Third, the formation of a tight heterostructure between mercaptofunctionalized perylene diimide and silver single-atom modified indium sulfide copper can promote the separation and transfer of photogenerated carriers and improve photocatalytic performance.

[0022] Fourth, this material exhibits good photocatalytic hydrogen peroxide production performance under both normal and hypoxic conditions, and is expected to be used for photocatalytic enhancement of copper ion release.

[0023] Fifth, this material promotes the release and accumulation of copper ions by generating hydrogen peroxide in situ, which is expected to further enhance the biological effects related to copper death. Attached Figure Description

[0024] Figure 1 This is a transmission electron microscope image of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide via self-oxygen supply, according to the present invention.

[0025] Figure 2The image shows the UV-Vis diffuse reflectance spectrum of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide via self-oxygen supply, according to the present invention.

[0026] Figure 3 This is an X-ray diffraction pattern of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide by self-oxygen supply according to the present invention.

[0027] Figure 4 The fluorescence spectrum of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide by self-supplying oxygen is shown in the present invention.

[0028] Figure 5 The photocurrent response diagram of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for producing hydrogen peroxide by self-oxygen supply according to the present invention is shown.

[0029] Figure 6 The image shows the photocatalytic activity of a heterojunction photocatalyst for producing hydrogen peroxide via self-oxygen supply, consisting of silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide.

[0030] Figure 7 This is a photocatalytic activity diagram of a heterojunction photocatalyst for hydrogen peroxide production by silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide, according to the present invention. Detailed Implementation

[0031] The specific embodiments of the present invention will now be described in detail with reference to the accompanying drawings, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0032] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated elements or components without excluding other elements or other components.

[0033] Specific Implementation Method 1: This implementation method describes the preparation of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst with self-oxygen-supplying hydrogen peroxide production capability, which is completed according to the following steps:

[0034] I. Preparation of copper indium sulfide nanoparticles:

[0035] Cuprous iodide and indium acetate were added to a mixed solvent of 1-octadecene and oleic acid to obtain a homogeneous dispersion. Then, 1-dodecylthiol was added as a sulfur source and coordinating ligand. The mixture was placed in a three-necked flask and heated under a nitrogen atmosphere to remove residual oxygen and moisture. After degassing, the reaction system was heated to 220°C and maintained for a certain time. After the reaction was completed, it was allowed to cool naturally to room temperature. The product was repeatedly precipitated and washed with chloroform and ethanol to finally obtain copper indium sulfide nanoparticles.

[0036] II. Preparation of silver single-atom modified copper indium sulfide nanoparticles:

[0037] Silver acetate and tributylphosphine were added to 1-octadecene and thoroughly mixed to form a silver precursor solution. Tributylphosphine can coordinate with silver ions, thereby regulating the reactivity of silver species and preventing rapid nucleation or formation of silver nanoparticles during the reaction. After cooling the copper indium sulfide nanoparticle reaction system to approximately 140°C, the above silver precursor solution was rapidly injected into the reaction system, and the reaction was continued for a certain period of time. After the reaction was completed, the product was collected by centrifugation, washed with a mixed solvent of chloroform and ethanol, and then dried to obtain silver single-atom modified copper indium sulfide nanoparticles.

[0038] III. Preparation of thiol-functionalized perylene diimide:

[0039] 3,4,9,10-Perylenetetracarboxylic dianhydride, imidazole, anhydrous zinc acetate, and 2-aminoethanethiol were mixed and reacted under an inert atmosphere with stirring. During the reaction, 3,4,9,10-Perylenetetracarboxylic dianhydride underwent an imidization reaction with molecules containing amino and thiol groups, introducing thiol functional groups. After the reaction was completed, ethanol and hydrochloric acid solution were added to the system to precipitate the product, which was then acidified to obtain a crude product. The crude product was repeatedly washed with ultrapure water until neutral and dried. Subsequently, the crude product was dispersed in water, and triethylamine was added to dissolve it completely, forming a homogeneous dark-colored solution. Hydrochloric acid solution was then added to induce molecular reassembly, and the resulting precipitate was collected, washed with water until neutral, and dried to obtain the final thiol-functionalized perylene diimide.

[0040] IV. Preparation of a heterojunction photocatalyst modified with silver single atoms and indium copper sulfide and thiol-functionalized perylene diimide:

[0041] The silver-modified indium copper sulfide nanoparticles obtained in step two and the thiol-functionalized perylene diimide obtained in Example three were dispersed separately in appropriate solvents and uniformly dispersed by ultrasonication or stirring. The two dispersions were then mixed to ensure sufficient contact between the silver-modified indium copper sulfide nanoparticles and the thiol-functionalized perylene diimide nanosheets. Through solvent exchange, self-assembly, or stirring, the uniform loading of the silver-modified indium copper sulfide nanoparticles onto the surface of the thiol-functionalized perylene diimide was promoted, forming a tightly contacted heterojunction interface. After the reaction was complete, the product was collected by centrifugation and washed with a suitable solvent to remove unbound components. The resulting product, after drying, yielded a silver-modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst.

[0042] Advantages of this implementation method:

[0043] I. The silver single-atom modified indium copper sulfide prepared in this invention can form a closely contacted heterostructure with thiol-functionalized perylene diimide to construct a Z-shaped heterostructure, which is beneficial to promote the separation and directional transfer of photogenerated carriers, reduce photogenerated electron-hole recombination, and thus improve the efficiency of photocatalytic reaction.

[0044] Second, the silver single-atom sites in copper sulfide modified with silver single atoms prepared in this invention can promote the capture and activation of oxygen, which is beneficial to improving the efficiency of oxygen reduction reaction and promoting the generation of hydrogen peroxide.

[0045] III. The silver single-atom modified copper indium sulfide / thiol-functionalized perylene diimide heterojunction nanomaterial prepared by this invention has good photocatalytic oxygen production capacity. Under light irradiation conditions, the oxygen production per gram of the photocatalyst can reach 4.5~9.8 mmol per hour.

[0046] IV. The silver single-atom modified copper indium sulfide / thiol-functionalized perylene diimide heterojunction nanomaterial prepared by this invention has the ability to generate hydrogen peroxide through self-oxygenation. Under normal oxygen conditions, each gram of the photocatalyst can generate 0.6 mmol to 1.8 mmol of hydrogen peroxide per hour.

[0047] V. The silver single-atom modified copper indium sulfide / thiol-functionalized perylene diimide heterojunction nanomaterial prepared in this invention still has the ability to produce hydrogen peroxide by photocatalysis under low oxygen or hypoxia conditions. The amount of hydrogen peroxide produced under low oxygen or hypoxia conditions can reach 30% to 70% of the amount of hydrogen peroxide produced under normal oxygen conditions, indicating that the material has good hypoxia tolerance photocatalytic performance.

[0048] This embodiment yields a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst that produces hydrogen peroxide through self-oxygen supply.

[0049] In this invention, single-atom modulation is an effective strategy for improving the catalytic performance of semiconductors. Introducing atomically dispersed metal sites into semiconductor materials can regulate the electronic structure of the material surface, improve the adsorption and activation capabilities of reactants, and increase the utilization efficiency of photogenerated carriers. Silver single-atom sites have the potential to regulate oxygen adsorption, promote oxygen activation, and optimize the oxygen reduction reaction pathway. Introducing silver single atoms into copper indium sulfide (CIS) materials is expected to improve their oxygen reduction reaction capability and increase the efficiency of hydrogen peroxide generation.

[0050] On the other hand, heterojunction engineering is also an important method to improve photocatalytic performance. By constructing suitable heterojunction structures, the spatial separation of photogenerated electrons and holes can be promoted, the carrier recombination probability can be reduced, and the redox capabilities of different components can be retained. Perylene diimide organic semiconductors have good light absorption capabilities, tunable molecular structures, and good potential for photocatalytic applications. Through thiol functionalization modification, perylene diimides can not only improve their own electronic structure, but also enhance their interfacial interactions with metal sulfide materials using thiol groups, thereby facilitating the construction of stable and efficient heterojunction structures.

[0051] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the molar ratio of cuprous iodide to indium acetate in step one is (0.5~2):(0.5~2); the mass of cuprous iodide is 0.05g~0.20g; and the mass of indium acetate is 0.08g~0.30g. The other steps are the same as in Specific Implementation Method One.

[0052] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that: the volume ratio of 1-octadecene to oleic acid in step one is (5~20):(0.5~3); the volume of 1-octadecene is 5mL~20mL; and the volume of oleic acid is 0.5mL~3mL. Other steps are the same as in Specific Implementation Method One or Two.

[0053] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that: the volume of 1-dodecyl mercaptan in step one is 2 mL to 10 mL; the 1-dodecyl mercaptan simultaneously serves as a sulfur source and a coordinating ligand. Other steps are the same as in Specific Implementation Methods One to Three.

[0054] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that: the degassing temperature in step one is 100℃~150℃; the degassing time is 10min~60min; and the protective atmosphere is nitrogen or argon. Other steps are the same as in Specific Implementation Methods One to Four.

[0055] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that: the heating rate in step one is 5℃ / min to 15℃ / min; the reaction temperature is 180℃ to 240℃; and the reaction time is 10min to 60min. Other steps are the same as in Specific Implementation Methods One to Five.

[0056] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that: in step two, silver acetate and tributylphosphine are added to 1-octadecene to form a silver precursor solution; the amount of silver acetate added is 0.001g~0.02g; the volume of tributylphosphine is 10μL~200μL; and the volume of 1-octadecene is 0.5mL~5mL. The other steps are the same as in Specific Implementation Methods One to Six.

[0057] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that: the silver precursor solution mentioned in step two is injected after the reaction system in step one has been cooled to 140℃~180℃; the injection method is rapid injection; and the continued reaction time is 10min~60min. Other steps are the same as in Specific Implementation Methods One to Seven.

[0058] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in the following ways: the centrifugation speed for centrifugation collection in step two is 6000 r / min to 12000 r / min, and the centrifugation time is 5 min to 20 min; the washing solvent is a mixed solvent of chloroform and ethanol; the volume ratio of chloroform to ethanol is 1:(1~5); the drying method is vacuum drying, the drying temperature is 40℃ to 80℃, and the drying time is 6 h to 24 h. Other steps are the same as in Specific Implementation Methods One to Eight.

[0059] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One to Nine in that: the amount of 3,4,9,10-perylenetetracarboxylic dianhydride used in step three is 1 mmol to 5 mmol; the mass of imidazole is 10 g to 40 g; the amount of anhydrous zinc acetate is 1 mmol to 5 mmol; and the amount of 2-aminoethanethiol is 2 mmol to 5 mmol. The other steps are the same as in Specific Implementation Methods One to Nine.

[0060] Specific Implementation Method Eleven: This implementation method differs from Specific Implementation Methods One through Ten in that: the inert atmosphere in step three is nitrogen or argon; the reaction temperature is 100℃~160℃; the reaction time is 2h~8h; and the stirring speed is 100r / min~500r / min. Other steps are the same as in Specific Implementation Methods One through Ten.

[0061] Specific Implementation Method Twelve: This implementation method differs from Specific Implementation Methods One to Eleven in that: the ethanol and hydrochloric acid solution mentioned in step three is used for acidification treatment; the volume of the ethanol is 50 mL to 200 mL; the concentration of the hydrochloric acid solution is 1 mol / L to 4 mol / L; the volume of the hydrochloric acid solution is 100 mL to 500 mL; and the acidification treatment time is 6 h to 24 h. The other steps are the same as in Specific Implementation Methods One to Eleven.

[0062] Specific Implementation Method Thirteen: This implementation method differs from Specific Implementation Methods One to Twelve in the following ways: the mass ratio of the crude product to water in step three is (0.1g~1.0g):(50mL~200mL); the volume of the triethylamine is 100μL~1000μL; the concentration of the hydrochloric acid solution is 2mol / L~6mol / L; the volume of the hydrochloric acid solution is 5mL~30mL; the induction recombination time is 1h~12h; the drying temperature is 40℃~80℃, and the drying time is 12h~48h. Other steps are the same as in Specific Implementation Methods One to Twelve.

[0063] Specific Implementation Method Fourteen: This implementation method differs from Specific Implementation Methods One to Thirteen in that: the volume ratio of the silver single-atom modified copper indium sulfide nanoparticle dispersion to the thiol-functionalized perylene diimide dispersion in step four is (2~5):(10~50); the dispersion solvent is one or a combination of several of water, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, and chloroform. Other steps are the same as in Specific Implementation Methods One to Thirteen.

[0064] Specific Implementation Method Fifteen: This implementation method differs from Specific Implementation Methods One to Fourteen in that: the ultrasonic frequency in step four is 40Hz~4000Hz, and the ultrasonic time is 5min~60min; the stirring speed is 100r / min~500r / min, and the stirring time is 10min~1h. Other steps are the same as in Specific Implementation Methods One to Fourteen.

[0065] Specific Implementation Method Sixteen: This implementation method differs from Specific Implementation Methods One to Fifteen in the following ways: the centrifugation speed for collection in step four is 6000 r / min to 12000 r / min, and the centrifugation time is 5 min to 20 min; the washing solvent is one or a combination of water, ethanol, chloroform, and N,N-dimethylformamide; the drying method is vacuum drying, the drying temperature is 40℃ to 80℃, and the drying time is 12 h to 48 h. Other steps are the same as in Specific Implementation Methods One to Fifteen.

[0066] The beneficial effects of the present invention are verified using the following embodiments:

[0067] Experiment 1: A method for preparing a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst that generates hydrogen peroxide through self-oxygen supply is carried out according to the following steps:

[0068] I. Preparation of copper indium sulfide nanoparticles:

[0069] Cuprous iodide and indium acetate were added to a mixed solvent of 1-octadecene and oleic acid to obtain a homogeneous dispersion. Then, 1-dodecylthiol was added as a sulfur source and coordinating ligand. The mixture was placed in a three-necked flask and heated under a nitrogen atmosphere to remove residual oxygen and moisture. After degassing, the reaction system was heated to 220°C and maintained for a certain time. After the reaction was completed, it was allowed to cool naturally to room temperature. The product was repeatedly precipitated and washed with chloroform and ethanol to finally obtain copper indium sulfide nanoparticles.

[0070] II. Preparation of silver single-atom modified copper indium sulfide nanoparticles:

[0071] Silver acetate and tributylphosphine were added to 1-octadecene and thoroughly mixed to form a silver precursor solution. Tributylphosphine can coordinate with silver ions, thereby regulating the reactivity of silver species and preventing rapid nucleation or formation of silver nanoparticles during the reaction. After cooling the copper indium sulfide nanoparticle reaction system to approximately 140°C, the above silver precursor solution was rapidly injected into the reaction system, and the reaction was continued for a certain period of time. After the reaction was completed, the product was collected by centrifugation, washed with a mixed solvent of chloroform and ethanol, and then dried to obtain silver single-atom modified copper indium sulfide nanoparticles.

[0072] III. Preparation of thiol-functionalized perylene diimide:

[0073] 3,4,9,10-Perylenetetracarboxylic dianhydride, imidazole, anhydrous zinc acetate, and 2-aminoethanethiol were mixed and reacted under an inert atmosphere with stirring. During the reaction, 3,4,9,10-Perylenetetracarboxylic dianhydride underwent an imidization reaction with molecules containing amino and thiol groups, introducing thiol functional groups. After the reaction was completed, ethanol and hydrochloric acid solution were added to the system to precipitate the product, which was then acidified to obtain a crude product. The crude product was repeatedly washed with ultrapure water until neutral and dried. Subsequently, the crude product was dispersed in water, and triethylamine was added to dissolve it completely, forming a homogeneous dark-colored solution. Hydrochloric acid solution was then added to induce molecular reassembly, and the resulting precipitate was collected, washed with water until neutral, and dried to obtain the final thiol-functionalized perylene diimide.

[0074] IV. Preparation of a heterojunction photocatalyst modified with silver single atoms and indium copper sulfide and thiol-functionalized perylene diimide:

[0075] The silver-modified indium copper sulfide nanoparticles obtained in step two and the thiol-functionalized perylene diimide obtained in Example three were dispersed separately in appropriate solvents and uniformly dispersed by ultrasonication or stirring. The two dispersions were then mixed to ensure sufficient contact between the silver-modified indium copper sulfide nanoparticles and the thiol-functionalized perylene diimide nanosheets. Through solvent exchange, self-assembly, or stirring, the uniform loading of the silver-modified indium copper sulfide nanoparticles onto the surface of the thiol-functionalized perylene diimide was promoted, forming a tightly contacted heterojunction interface. After the reaction was complete, the product was collected by centrifugation and washed with a suitable solvent to remove unbound components. The resulting product, after drying, yielded a silver-modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst.

[0076] The 3,4,9,10-perylenetetracarboxylic acid dianhydride described in this embodiment was purchased from Alfaesa (China) Chemical Co., Ltd.

[0077] Figure 1 Transmission electron microscope image of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared for Experiment 1, which produces hydrogen peroxide through self-oxygen supply.

[0078] Depend on Figure 1 It can be seen that the silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared in Experiment 1 exhibits a nanosheet structure as a whole. The silver single-atom modified indium copper sulfide nanoparticles can be loaded on the surface of thiol-functionalized perylene diimide nanosheets, indicating that the two were successfully combined and formed a heterojunction structure.

[0079] Figure 2 The UV-Vis diffuse reflectance spectrum of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared for Experiment 1, which generates hydrogen peroxide through self-oxygen supply.

[0080] Depend on Figure 2 It can be seen that the silver single-atom modified copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst prepared in Experiment 1 has a wide spectral absorption range, which can be extended from the visible light region to the near-infrared light region, indicating that the heterojunction nanomaterial has good broad spectral response capability.

[0081] Figure 3 X-ray photoelectron spectroscopy (XPS) of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared for Experiment 1, which generates hydrogen peroxide through self-oxygen supply.

[0082] Depend on Figure 3It can be seen that in the silver single-atom modified copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst prepared in Experiment 1, Ag mainly exists in the ionic form, indicating that the silver species do not aggregate in large quantities in the form of metallic silver particles, but can exist in a highly dispersed state in the copper sulfide material.

[0083] Figure 4 The fluorescence spectrum of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared for Experiment 1, which produces hydrogen peroxide through self-oxygen supply.

[0084] Depend on Figure 4 It can be seen that, compared with the single component, the fluorescence intensity of the silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst prepared in Experiment 1 is significantly reduced, indicating that the silver single-atom modification and the construction of the heterojunction structure are beneficial to suppressing photogenerated electron-hole recombination and promoting the separation and transfer of photogenerated charge carriers.

[0085] Figure 5 Photocurrent response diagram of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared for Experiment 1, which generates hydrogen peroxide through self-oxygen supply.

[0086] Depend on Figure 5 It can be seen that the silver single-atom modified copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst prepared in Experiment 1 has a strong and stable photocurrent response, indicating that the silver single-atom modification and the introduction of the heterojunction structure can promote the separation and transport of photogenerated charges and give the material a certain photostability.

[0087] The photocatalytic oxygen evolution experiment of a silver single-atom modified indium copper sulfide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production via experiment 1 is as follows:

[0088] The photocatalytic oxygen evolution reaction (OER) was carried out using an integrated system consisting of a photoreactor and an online analysis system, specifically a Labsolar-6A circulating system. A certain amount of photocatalyst was dispersed in 100 mL of aqueous solution, with AgNO3 added as an electron acceptor and La2O3 as a pH buffer. Before the reaction, dissolved gases in the aqueous solution were removed by vacuuming to ensure the reaction system was deoxygenated. Subsequently, the photocatalytic reaction was carried out under 300W xenon lamp irradiation, and the O2 content generated during the reaction was detected using an online gas chromatograph.

[0089] Figure 6 Photocatalytic oxygen production activity diagram of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared for Experiment 1, which produces hydrogen peroxide through self-oxygen supply.

[0090] Depend on Figure 6It is evident that the silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared in Experiment 1 exhibits excellent water oxidation oxygen production capability, indicating that this material can generate oxygen through water oxidation under light conditions, thereby providing an oxygen source for subsequent oxygen reduction to produce hydrogen peroxide. This result demonstrates that silver single-atom modification and the construction of the heterojunction structure are beneficial for realizing the photocatalytic self-supplying oxygen hydrogen peroxide production process.

[0091] The photocatalytic hydrogen peroxide production experiment of a silver single-atom modified indium copper sulfide heterojunction photocatalyst with thiol-functionalized perylene diimide prepared in Experiment 1, which produces hydrogen peroxide through self-oxygen supply, is as follows:

[0092] A certain amount of silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst were ultrasonically dispersed in deionized water to obtain a uniform dispersion. The resulting dispersion was placed in a reaction vessel and subjected to photoreaction under specific atmospheric conditions. After a certain reaction time, the reaction solution was filtered, and the filtrate was collected for hydrogen peroxide content detection.

[0093] Hydrogen peroxide content was determined using the iodometric method. The specific steps were as follows: a certain amount of filtrate was taken, potassium iodide solution and potassium hydrogen phthalate solution were added, and the mixture was left to stand in the dark for a certain period of time. Under acidic conditions, H₂O₂ reacts with I₂... - The reaction produces I3 - The reaction is as follows: H₂O₂ + 3I₂ - +2H + →I3 - + 2H2O, in the generated I3 - It has a distinct absorption peak at about 350 nm, so the absorbance of the solution at 350 nm can be determined by UV-Vis absorption spectroscopy, and the amount of hydrogen peroxide generated in the reaction system can be calculated according to the standard curve.

[0094] Figure 7 The photocatalytic hydrogen peroxide production activity diagram of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared for Experiment 1, which produces hydrogen peroxide through self-oxygen supply, under normal oxygen and oxygen-deficient conditions.

[0095] Depend on Figure 7 It was found that the silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared in Experiment 1 exhibited good photocatalytic hydrogen peroxide production capabilities under both normal and hypoxic conditions. This result indicates that the heterojunction nanomaterial can not only generate hydrogen peroxide using the oxygen reduction reaction under normal oxygen conditions, but also replenish oxygen in situ through water oxidation under hypoxic conditions, and further utilize the generated oxygen for the oxygen reduction reaction to generate hydrogen peroxide. This demonstrates that silver single-atom modification and the construction of the heterojunction structure can improve oxygen utilization efficiency and facilitate the realization of a self-supplied oxygen hydrogen peroxide production process.

[0096] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A method for preparing a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production, characterized in that, Includes the following steps: I. Preparation of copper indium sulfide nanoparticles: Cuprous iodide and indium acetate were added to a mixed solvent of 1-octadecene and oleic acid and stirred to disperse, resulting in a uniform dispersion system. Subsequently, 1-dodecylthiol was added as a sulfur source and coordinating ligand, and the mixture was stirred and mixed again. The mixture was placed in a three-necked flask and heated under a nitrogen atmosphere to remove residual oxygen and moisture. After degassing, the reaction system was heated to the reaction temperature and maintained. After the reaction was completed, the mixture was naturally cooled to room temperature, and the product was repeatedly precipitated and washed with chloroform and ethanol. After drying, copper indium sulfide nanoparticles were obtained. II. Preparation of silver single-atom modified copper indium sulfide nanoparticles: Silver acetate and tributylphosphine were added to 1-octadecene and mixed thoroughly to form a silver precursor solution. After the reaction system of copper indium sulfide nanoparticles in step one cooled down, the silver precursor solution was rapidly injected into the reaction system and the reaction continued. After the reaction was completed, the product was collected by centrifugation, washed with a mixed solvent of chloroform and ethanol, and then dried to obtain silver single-atom modified copper indium sulfide nanoparticles. III. Preparation of thiol-functionalized perylene diimide: 3,4,9,10-perylenetetracarboxylic acid dianhydride, imidazole, anhydrous zinc acetate, and 2-aminoethanethiol were mixed and reacted under an inert atmosphere with stirring. After the reaction was completed, ethanol and hydrochloric acid solution were added to the system to precipitate the product and acidify it to obtain a crude product. The crude product was repeatedly washed with ultrapure water until neutral and dried. Subsequently, the crude product was dispersed in water, and triethylamine was added to dissolve it completely to form a homogeneous solution. Hydrochloric acid solution was added to induce molecular reassembly. The resulting precipitate was collected, washed with water until neutral, and then dried to obtain thiol-functionalized perylene diimide. IV. Preparation of a heterojunction photocatalyst modified with silver single atoms and indium copper sulfide and thiol-functionalized perylene diimide: The silver-modified copper sulfide nanoparticles obtained in step two and the thiol-functionalized perylene diimide obtained in step three were dispersed separately in a solvent and uniformly dispersed by ultrasonication or stirring. The two dispersions were then mixed to ensure sufficient contact between the silver-modified copper sulfide nanoparticles and the thiol-functionalized perylene diimide. Through solvent exchange, self-assembly, or stirring, the silver-modified copper sulfide nanoparticles were uniformly loaded onto the surface of the thiol-functionalized perylene diimide, forming a tightly contacted heterojunction interface. After the reaction was complete, the product was collected by centrifugation and washed with a suitable solvent to remove unbound components. The resulting product was dried to obtain a silver-modified copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst with the ability to produce hydrogen peroxide through self-oxygenation.

2. The preparation method of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production according to claim 1, characterized in that, In step one, the molar ratio of cuprous iodide to indium acetate is (0.5~2):(0.5~2); the mass of cuprous iodide in step one is 0.05g~0.20g; the mass of indium acetate in step one is 0.08g~0.30g. In step one, the volume ratio of 1-octadecene to oleic acid is (5~20):(0.5~3); the volume of 1-octadecene in step one is 5mL~20mL; the volume of oleic acid in step one is 0.5mL~3mL. In step one, the volume of 1-dodecyl mercaptan is 2 mL to 10 mL; in step one, 1-dodecyl mercaptan serves as both a sulfur source and a coordinating ligand.

3. The preparation method of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production according to claim 1, characterized in that, The degassing temperature in step one is 100℃~150℃; the degassing time in step one is 10min~60min; the protective atmosphere in step one is nitrogen or argon. The heating rate in step one is 5℃ / min to 15℃ / min; the reaction temperature in step one is 180℃ to 240℃; and the reaction time in step one is 10min to 60min.

4. The preparation method of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production according to claim 1, characterized in that, In step two, the silver precursor solution is obtained by mixing silver acetate, tributylphosphine, and 1-octadecene; the amount of silver acetate added in step two is 0.001 g to 0.02 g; the volume of tributylphosphine in step two is 10 μL to 200 μL; and the volume of 1-octadecene in step two is 0.5 mL to 5 mL. In step two, the silver precursor solution is injected after the reaction system in step one has been cooled to 140℃~180℃; the injection method in step two is rapid injection; the reaction time in step two is 10min~60min.

5. The preparation method of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production according to claim 1, characterized in that, In step two, the centrifugation speed for collection is 6000 r / min to 12000 r / min, and the centrifugation time is 5 min to 20 min. In step two, the washing solvent is a mixture of chloroform and ethanol. In step two, the volume ratio of chloroform to ethanol is 1:(1 to 5). In step two, the drying method is vacuum drying, the drying temperature is 40℃ to 80℃, and the drying time is 6 h to 24 h.

6. The preparation method of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production according to claim 1, characterized in that, In step three, the amount of 3,4,9,10-perylenetetracarboxylic acid dianhydride used is 1 mmol to 5 mmol; the mass of imidazole in step three is 10 g to 40 g; the amount of anhydrous zinc acetate in step three is 1 mmol to 5 mmol; and the amount of 2-aminoethanethiol in step three is 2 mmol to 5 mmol. In step three, the inert atmosphere is nitrogen or argon; the reaction temperature in step three is 100℃~160℃; the reaction time in step three is 2h~8h; and the stirring speed in step three is 100r / min~500r / min.

7. The preparation method of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production according to claim 1, characterized in that, In step three, ethanol and hydrochloric acid solution are used for acidification treatment; the volume of ethanol in step three is 50 mL to 200 mL; the concentration of hydrochloric acid solution in step three is 1 mol / L to 4 mol / L; the volume of hydrochloric acid solution in step three is 100 mL to 500 mL; and the acidification treatment time in step three is 6 h to 24 h. In step three, the mass ratio of crude product to water is (0.1g~1.0g):(50mL~200mL); the volume of triethylamine in step three is 100μL~1000μL; the concentration of hydrochloric acid solution in step three is 2mol / L~6mol / L; the volume of hydrochloric acid solution in step three is 5mL~30mL; the induction recombination time in step three is 1h~12h; the drying temperature in step three is 40℃~80℃, and the drying time is 12h~48h.

8. The preparation method of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production according to claim 1, characterized in that, In step four, the volume ratio of the silver single-atom modified copper indium sulfide nanoparticle dispersion to the thiol-functionalized perylene diimide dispersion is (2~5):(10~50); the dispersion solvent in step four is one or a combination of several of water, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, and chloroform. In step four, the ultrasonic frequency is 40Hz~4000Hz and the ultrasonic time is 5min~60min; the stirring speed in step four is 100r / min~500r / min and the stirring time is 10min~1h.

9. The preparation method of a silver single-atom modified indium copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst for self-oxygenated hydrogen peroxide production according to claim 1, characterized in that, In step four, the centrifugation speed for collection is 6000 r / min to 12000 r / min, and the centrifugation time is 5 min to 20 min. The washing solvent in step four is one or a combination of water, ethanol, chloroform, and N,N-dimethylformamide. The drying method in step four is vacuum drying, with a drying temperature of 40℃ to 80℃ and a drying time of 12 h to 48 h.

10. The application of a silver single-atom modified indium copper sulfide and thiol-functionalized perylene diimide heterojunction photocatalyst prepared by the preparation method according to any one of claims 1-9, characterized in that, The silver single-atom modified copper sulfide and mercapto-functionalized perylene diimide heterojunction photocatalyst is used as a photocatalyst for photocatalytic oxygen production and photocatalytic hydrogen peroxide production, or for photocatalytic enhancement of copper ion release, or for the preparation of copper death-enhancing materials.

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