Manganese-doped cu7s4 nanomaterials, methods of making and applications thereof

Abstract

The application discloses a manganese-doped Cu7S4 nanomaterial and a preparation method and application thereof. The manganese-doped Cu7S4 nanomaterial comprises a Cu7S4 nanomaterial and manganese elements doped in the Cu7S4 nanomaterial, and the manganese-doped Cu7S4 nanomaterial has an enzyme-like catalytic performance. The preparation method comprises the following steps: reacting a mixed reaction system containing Cu2O, polyvinylpyrrolidone, a manganese salt and a hydroxide to obtain a Cu2O / Mn(OH)2 composite; and then reacting NaHS to obtain the manganese-doped Cu7S4 nanomaterial. The manganese-doped Cu7S4 nanomaterial provided by the application has a unique and novel structure, higher enzyme-like catalytic effect, high stability, long-term storage, and is beneficial to clinical application of tumors, and the preparation method is simple and easy to implement, low in cost, universal and beneficial to large-scale production.

Description

Technical Field

[0001] This invention relates to a Cu7S4 nanomaterial, and more particularly to a manganese-doped Cu7S4 nanomaterial, its preparation method and application, belonging to the field of materials science. Background Technology

[0002] Copper sulfide nanomaterials have broad application prospects in novel tumor diagnosis and treatment due to their strong near-infrared optical absorption and enzyme-like catalytic activity highly sensitive to the tumor microenvironment. However, some literature reports that the enzyme-like activity of copper sulfide materials is strongly pH-dependent, and the pH value of the typical tumor microenvironment cannot fully meet its requirements, thereby reducing the catalytic activity of these materials and limiting their application in tumor therapy. Summary of the Invention

[0003] The main objective of this invention is to provide a manganese-doped Cu7S4 nanomaterial, its preparation method, and its application, so as to overcome the shortcomings of the prior art.

[0004] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0005] This invention provides a manganese-doped Cu7S4 nanomaterial, comprising: Cu7S4 nanomaterial and manganese element doped in the Cu7S4 nanomaterial, wherein the manganese content in the manganese-doped Cu7S4 nanomaterial is 0.05wt% to 1wt%, and the manganese-doped Cu7S4 nanomaterial has enzyme-like catalytic properties.

[0006] This invention also provides a method for preparing manganese-doped Cu7S4 nanomaterials, comprising:

[0007] A first reaction was carried out on a mixed reaction system containing Cu2O, polyvinylpyrrolidone, manganese salt and hydroxide to prepare Cu2O / Mn(OH)2 complex.

[0008] Furthermore, the Cu2O / Mn(OH)2 composite is subjected to a second reaction with NaHS to obtain manganese-doped Cu7S4 nanomaterials.

[0009] This invention also provides the use of the aforementioned manganese-doped Cu7S4 nanomaterials in the preparation of nanoenzyme materials.

[0010] Compared with the prior art, the technical solution of the present invention has at least the following advantages:

[0011] The manganese-doped Cu7S4 nanomaterials provided by this invention have a unique and novel structure. Through Mn doping, the material exhibits a higher enzyme-like catalytic effect, high stability, and long-term storage, which is beneficial for clinical applications in tumors. Furthermore, this invention proposes a simple and mild wet chemical method for preparing manganese-doped Cu7S4 nanomaterials at room temperature. This preparation method is simple to implement, low in cost, universal, and conducive to large-scale production. Attached Figure Description

[0012] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0013] Figure 1 This is a transmission electron microscope image of the Cu2O nanospheres obtained in Example 1 of this invention;

[0014] Figure 2 These are transmission electron microscope images of the Cu2O@Mn(OH)2 nanomaterials obtained in Example 1 of this invention;

[0015] Figure 3 This is a transmission electron microscope image of the manganese-doped Cu7S4 nanomaterial obtained in Example 1 of this invention;

[0016] Figures 4a-4c These are scanning electron microscope (SEM) images of Cu2O nanospheres, Cu2O@Mn(OH)2 nanomaterials, and manganese-doped Cu7S4 nanospheres obtained in Example 1 of this invention, respectively.

[0017] Figures 5a-5e These are electron microscopy energy dispersive spectroscopy mapping images of the manganese-doped Cu7S4 nanomaterials obtained in Example 1 of this invention.

[0018] Figure 6 These are polycrystalline X-ray diffraction images of Cu2O nanospheres, Cu2O@Mn(OH)2 nanomaterials, and manganese-doped Cu7S4 nanospheres obtained in Example 1 of this invention;

[0019] Figure 7 These are Zeta potential images of Cu2O nanospheres, Cu2O@Mn(OH)2 nanomaterials, and manganese-doped Cu7S4 nanospheres obtained in Example 1 of this invention;

[0020] Figure 8a and Figure 8bThese are X-ray photoelectron spectroscopy images of Cu2O nanospheres, Cu2O@Mn(OH)2 nanomaterials and manganese-doped Cu7S4 nanospheres obtained in Example 1 of this invention;

[0021] Figures 9a-9f This is a graph showing the results of measuring the catalytic activity of manganese-doped Cu7S4 nanospheres in Example 1 of this invention. Detailed Implementation

[0022] To address the shortcomings of the aforementioned copper sulfide materials, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention. The main approach involves ion doping, which introduces electron-hole pairs, thereby promoting electron transport on the material surface and enhancing its catalytic activity. Based on this principle, the inventors have proposed a method for preparing manganese-doped Cu7S4 nanomaterials at room temperature via a simple and mild wet chemical process. Through Mn doping, this material exhibits higher catalytic activity, potentially improving its clinical application value. The following will further explain the technical solution, its implementation process, and its principles.

[0023] One aspect of the present invention provides a manganese-doped Cu7S4 nanomaterial comprising: Cu7S4 nanomaterial and manganese element doped in the Cu7S4 nanomaterial, wherein the manganese-doped Cu7S4 nanomaterial has excellent enzyme-like catalytic performance.

[0024] In some embodiments, the manganese content in the manganese-doped Cu7S4 nanomaterial is 0.05 wt% to 1.0 wt%.

[0025] In some embodiments, the manganese-doped Cu7S4 nanomaterials have nanometer-scale dimensions. Further, the diameter of the manganese-doped Cu7S4 nanomaterials is 80–120 nm.

[0026] In some embodiments, the manganese-doped Cu7S4 nanomaterial is spherical in shape, and its spherical shape remains unchanged for 0.5 to 2 hours, maintaining its shape well.

[0027] In some embodiments, the manganese-doped Cu7S4 nanomaterials are synthesized at room temperature.

[0028] The inventors of this case also studied the details of the parameters required to prepare manganese-doped Cu7S4 nanostructures and obtained for the first time the parameters required to synthesize manganese-doped Cu7S4 nanostructures.

[0029] Specifically, another aspect of the present invention provides a method for preparing manganese-doped Cu7S4 nanomaterials, comprising:

[0030] A first reaction was carried out on a mixed reaction system containing Cu2O, polyvinylpyrrolidone, manganese salt and hydroxide to prepare Cu2O / Mn(OH)2 complex.

[0031] Furthermore, the Cu2O / Mn(OH)2 composite is subjected to a second reaction with NaHS to obtain manganese-doped Cu7S4 nanomaterials.

[0032] In some embodiments, the manganese salt may include any one or a combination of two of manganese dichloride (MnCl2), manganese acetate, etc., but is not limited thereto.

[0033] In some embodiments, the hydroxide may include any one or a combination of two of sodium hydroxide (NaOH), potassium hydroxide (KOH), etc., but is not limited thereto.

[0034] Furthermore, the polyvinylpyrrolidone used in this invention as a surfactant can help adjust the uniformity of the product.

[0035] In some embodiments, the first reaction is carried out at room temperature for 12 to 36 hours.

[0036] In some embodiments, the second reaction is carried out at room temperature for 0.5 to 2 hours.

[0037] In some more specific implementation schemes, the preparation method of the manganese-doped Cu7S4 nanomaterials mainly includes the following steps:

[0038] (1) At room temperature, Cu2O was added to anhydrous ethanol, and polyvinylpyrrolidone K30 was added after 10 minutes. MnCl2 and NaOH were added to the above solution with stirring, and the mixture was allowed to stand overnight. After centrifugation and washing, Cu2O / Mn(OH)2 complex (which can be labeled as Cu2O@Mn(OH)2) was obtained.

[0039] (2) At room temperature, the prepared Cu2O@Mn(OH)2 was dispersed in water to form a dispersion, NaHS was added and stirred to react, and after centrifugation, it was dried and washed to obtain Mn-doped Cu7S4 nanospheres.

[0040] In some implementations, in step (1), the mixed reaction system includes Cu2O at a concentration of 0.5–1.0 mg / mL, polyvinylpyrrolidone K30 at a concentration of 40–80 mg / mL, manganese salt (MnCl2) at a concentration of 0.2–0.4 mg / mL, and hydroxide (NaOH) at a concentration of 5–10 mg / mL.

[0041] In some implementation schemes, in step (2), the molar ratio of the Cu2O / Mn(OH)2 complex to NaHS is 1:2 to 1:3.

[0042] Furthermore, in step (2), the concentration of NaHS added is 0.8–1.5 mg / mL, and the stirring time is 0.5–2 hours.

[0043] In summary, the manganese-doped Cu7S4 nanomaterials prepared by this invention have excellent enzyme-like catalytic performance, high stability, and can be stored for a long time. At the same time, their preparation is simple and easy to implement, low in cost, and has universality, which is conducive to large-scale production.

[0044] Another aspect of the present invention provides the application of the aforementioned manganese-doped Cu7S4 nanomaterials in the preparation of nanoenzyme materials.

[0045] Furthermore, another aspect of the present invention provides the use of the aforementioned manganese-doped Cu7S4 nanomaterials in enzyme-like catalysis.

[0046] Accordingly, another aspect of the present invention provides a nanoenzyme material comprising any of the aforementioned manganese-doped Cu7S4 nanomaterials.

[0047] The present invention will be further illustrated by the following embodiments and accompanying drawings: The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the specific material ratios, process conditions, and results described in the embodiments are for illustrative purposes only and should not, and will not, limit the present invention as described in detail in the claims.

[0048] Unless otherwise specified, the various raw materials, reaction equipment, testing equipment and testing methods used in the following embodiments are all known in the art.

[0049] Example 1

[0050] refer to Figure 1 As shown, a method for preparing manganese-doped Cu7S4 nanomaterials includes the following steps:

[0051] (a) At room temperature, 36 mg of the prepared Cu2O was added to 40 ml of anhydrous ethanol, and 2 g of polyvinylpyrrolidone K30 was added after 10 minutes. 10 mg of MnCl2 and 0.32 g of NaOH were added to the above solution with stirring, and the mixture was allowed to stand overnight. After centrifugation and washing, Cu2O@Mn(OH)2 was obtained.

[0052] (b) At room temperature, the prepared Cu2O@Mn(OH)2 was dispersed in water to form a dispersion, and NaHS (0.8-1.5 mg / mL) was added and stirred for 1.5 h. After centrifugation, the mixture was dried and washed to obtain Mn-doped Cu7S4 nanospheres (Mn content of 0.15 wt%).

[0053] The inventors in this case also tested various properties of the obtained Mn-doped Cu7S4 nanospheres, and the results are as follows:

[0054] Figure 1 The image shown is a transmission electron microscope image of the Cu2O nanosphere sample obtained in this embodiment. It can be seen that spherical Cu2O with a size of approximately 80-120 nm was synthesized.

[0055] Figure 2 The image shows a transmission electron microscope (TEM) image of the Cu2O@Mn(OH)2 nanomaterial obtained in this embodiment. It can be seen that when MnCl2 is added, durian-shaped nanoparticles can be observed in the image, indicating that Mn(OH)2 is formed on the surface of Cu2O.

[0056] Figure 3 The image shown is a transmission electron microscope image of the manganese-doped Cu7S4 nanomaterials obtained in this embodiment. It can be seen that after the introduction of NaHS, the needle-like NPs are transformed into nanosheets on the surface of the nanospheres, indicating Cu2O@Mn(OH)2 sulfidation.

[0057] Figures 4a-4c The images show scanning electron microscope (SEM) images of Cu2O nanospheres, Cu2O@Mn(OH)2 nanomaterials, and the obtained manganese-doped Cu7S4 nanomaterials in this embodiment. The formation and sulfidation process of Cu2O@Mn(OH)2 can be seen in the images.

[0058] Figures 5a-5e This is an X-ray energy dispersive spectroscopy (EDS) mapping analysis image of the manganese-doped Cu7S4 nanomaterials obtained in this embodiment. The manganese-doped Cu7S4 nanomaterials obtained after Cu2O@Mn(OH)2 sulfidation show that in addition to copper, oxygen, and manganese, sulfur is also present, proving that manganese-doped Cu7S4 nanomaterials have been obtained. Copper is represented by blue, oxygen by red, manganese by yellow, and sulfur by orange.

[0059] Figure 6 The images show the polycrystalline X-ray diffraction patterns of the Cu2O nanospheres, Cu2O@Mn(OH)2 nanomaterials, and manganese-doped Cu7S4 nanospheres obtained in this embodiment. The phase transformation of the materials and the formation of manganese-doped Cu7S4 nanomaterials can be clearly seen from the images.

[0060] Figure 7The images show the Zeta potentials of the Cu₂O nanospheres, Cu₂O@Mn(OH)₂ nanomaterials, and manganese-doped Cu₇S₄ nanospheres obtained in this example. It can be seen that the Zeta potential of Cu₂O is -22.54 mV, while that of Cu₂O@Mn(OH)₂ increases to 7.72 mV. The increase in Zeta potential confirms the presence of Mn(OH)₂. After sulfidation, the Zeta potential changes significantly (to -22.07 mV), confirming the preparation of manganese-doped Cu₇S₄ nanomaterials.

[0061] Figure 8a and Figure 8b These are X-ray photoelectron spectroscopy (XPS) images of the Cu₂O nanospheres, Cu₂O@Mn(OH)₂ nanomaterials, and manganese-doped Cu₇S₄ nanospheres obtained in this embodiment. Compared to the three elements (copper, manganese, and oxygen) in Cu₂O@Mn(OH)₂, the manganese-doped Cu₇S₄ nanomaterials include four elements: copper, manganese, oxygen, and sulfur.

[0062] Figures 9a-9f This is a graph showing the results of measuring the enzyme-like catalytic activity of manganese-doped Cu7S4 nanospheres in this embodiment. Figure 9a The results indicate that the prepared manganese-doped Cu7S4 nanomaterials exhibit excellent pH-sensitive catalytic activity for TMB oxidation, showing higher ·OH generation capacity under acidic conditions than under neutral conditions. Furthermore, under the same conditions, the TMB absorbance of manganese-doped Cu7S4 nanomaterials and H2O2 is 1.5 times and 4 times higher than that of Cu2O and Cu2O@Mn(OH)2, respectively, indicating higher catalytic performance after the introduction of Mn and sulfidation. Figure 9b This indicates that even when its concentration is reduced to 1 μg / mL, it still exhibits significant catalytic activity. For example... Figure 9c As shown, copper and manganese-based nanomaterials can initiate a Fenton-like reaction to generate ·OH ions. Figure 9d and Figure 9e When manganese-doped Cu7S4 nanomaterials were added, the absorption of MB decreased rapidly, further demonstrating the excellent ·OH generation ability of manganese-doped Cu7S4 nanomaterials. EPR experiments also confirmed these results. Figure 9f In the study, the number of ·OH signals found in manganese-doped Cu7S4 nanomaterials was far greater than that found in Cu2O@Mn(OH)2 and pure H2O2.

[0063] Example 2: A method for preparing manganese-doped Cu7S4 nanomaterials includes the following steps:

[0064] (a) At room temperature, 36 mg of the prepared Cu2O was added to 40 ml of anhydrous ethanol, and 2 g of polyvinylpyrrolidone K30 was added after 10 minutes. 10 mg of MnCl2 and 0.32 g of NaOH were added to the above solution with stirring, and the mixture was allowed to stand overnight. After centrifugation and washing, Cu2O@Mn(OH)2 was obtained.

[0065] (b) At room temperature, the prepared Cu2O@Mn(OH)2 was dispersed in water to form a dispersion, and NaHS (0.8 mg / mL) was added and stirred for 0.5 h. After centrifugation, the mixture was dried and washed to obtain Mn-doped Cu7S4 nanospheres.

[0066] Example 3: A method for preparing manganese-doped Cu7S4 nanomaterials includes the following steps:

[0067] (a) At room temperature, 40 mg of the prepared Cu2O was added to 40 ml of anhydrous ethanol, and 1.6 g of polyvinylpyrrolidone K30 was added after 10 minutes. 8 mg of manganese acetate and 0.2 g of KOH were added to the above solution with stirring, and the mixture was allowed to stand overnight for 24 h. After centrifugation and washing, Cu2O@Mn(OH)2 was obtained.

[0068] (b) At room temperature, the prepared Cu2O@Mn(OH)2 was dispersed in water to form a dispersion, and NaHS was added and stirred for 2 h. The molar ratio of Cu2O@Mn(OH)2 to NaHS was 1:2. After centrifugation, the mixture was dried and washed to obtain Mn-doped Cu7S4 nanospheres.

[0069] Example 4: A method for preparing manganese-doped Cu7S4 nanomaterials includes the following steps:

[0070] (a) At room temperature, 20 mg of the prepared Cu2O was added to 40 ml of anhydrous ethanol, and 3.2 g of polyvinylpyrrolidone K30 was added after 10 minutes. 16 mg of MnCl2 and 0.4 g of NaOH were added to the above solution with stirring, and the mixture was allowed to stand overnight for 12 h. After centrifugation and washing, Cu2O@Mn(OH)2 was obtained.

[0071] (b) At room temperature, the prepared Cu2O@Mn(OH)2 was dispersed in water to form a dispersion, and NaHS was added and stirred for 1.5 h. The molar ratio of Cu2O@Mn(OH)2 to NaHS was 1:3. After centrifugation, the mixture was dried and washed to obtain Mn-doped Cu7S4 nanospheres.

[0072] The inventors of this case also tested the performance of the Mn-doped Cu7S4 nanospheres obtained in Examples 2-4, and the results showed that they were basically consistent with those in Example 1.

[0073] Comparative Example 1

[0074] The preparation method of the manganese-doped Cu7S4 nanomaterials in this comparative example is basically the same as that in Example 1, except that the reaction was stirred overnight in step (b). The resulting product sample has a non-uniform spherical structure with some nanosheets.

[0075] Comparative Example 2

[0076] This comparative example is undoped copper sulfide nanomaterials. The specific method is as follows: at room temperature, 36 mg of the prepared Cu2O was added to 40 ml of anhydrous ethanol. After 10 minutes, 2 g of polyvinylpyrrolidone K30 was added, and NaHS (1 mg / mL) was added and stirred for 1.5 h. After centrifugation, the mixture was dried and washed to obtain copper sulfide nanospheres.

[0077] The result was copper sulfide nanospheres, and their catalytic performance was not as good as that of the doped nanomaterials.

[0078] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0079] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the described embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims.

Claims

1. A method for preparing manganese-doped Cu7S4 nanomaterials, characterized in that, include: A first reaction was carried out on a mixed reaction system containing Cu2O, polyvinylpyrrolidone, manganese salt and hydroxide to prepare Cu2O / Mn(OH)2 complex. Furthermore, the Cu2O / Mn(OH)2 composite is subjected to a second reaction with NaHS to obtain manganese-doped Cu7S4 nanomaterials; The manganese-doped Cu7S4 nanomaterial comprises: Cu7S4 nanomaterial, and manganese element doped in the Cu7S4 nanomaterial, wherein the manganese content in the manganese-doped Cu7S4 nanomaterial is 0.05 wt%~1 wt%, and the manganese-doped Cu7S4 nanomaterial has enzyme-like catalytic properties.

2. The preparation method according to claim 1, characterized in that: The mixed reaction system includes Cu2O at a concentration of 0.5–1.0 mg / mL, polyvinylpyrrolidone at a concentration of 40–80 mg / mL, manganese salt at a concentration of 0.2–0.4 mg / mL, and hydroxide at a concentration of 5–10 mg / mL.

3. The preparation method according to claim 1 or 2, characterized in that: The manganese salt is selected from at least one of manganese dichloride and manganese acetate.

4. The preparation method according to claim 1 or 2, characterized in that: The hydroxide is selected from at least one of sodium hydroxide and potassium hydroxide.

5. The preparation method according to claim 1, characterized in that: The first reaction was carried out at room temperature for 12 to 36 hours.

6. The preparation method according to claim 1, characterized in that: The molar ratio of the Cu2O / Mn(OH)2 complex to NaHS is 1:2 to 1:

3.

7. The preparation method according to claim 1, characterized in that: The second reaction was carried out at room temperature for 0.5 to 2 hours.

8. The preparation method according to claim 1, characterized in that: The diameter of the manganese-doped Cu7S4 nanomaterial is 80~120 nm.

9. The preparation method according to claim 1, characterized in that: The manganese-doped Cu7S4 nanomaterials are spherical and remain unchanged for 0.5 to 2 hours.

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