Preparation method of nano cuprous sulfide and nano cuprous sulfide

Abstract

The invention provides a preparation method of nano cuprous sulfide and the nano cuprous sulfide, and particularly relates to the technical field of preparation of inorganic nano materials. The preparation method of the nano cuprous sulfide comprises the following steps: adding a sulfur source solution into an acidic complex solution of cuprous ions to obtain an intermediate suspension; then carrying out ultrasonic reaction on the intermediate suspension, continuing to react for 1-2 hours after the system becomes black suspension, then stopping the reaction, and carrying out solid-liquid separation on the system to obtain a precipitate; and finally, washing the precipitate, and carrying out vacuum drying to obtain the nano cuprous sulfide. Wherein a sulfur source in the sulfur source solution comprises a thioamide compound. According to the preparation method, the intermediate suspension serving as a precursor of cuprous sulfide has good stability, formation and conversion of an intermediate are promoted under the ultrasonic action, the particle size of nano cuprous sulfide is effectively controlled, and the nano cuprous sulfide is uniform in distribution, small in size and good in uniformity and dispersity.

Description

Technical Field

[0001] The invention relates to the technical field of inorganic nano material preparation, in particular to a preparation method of nano cuprous sulfide and the nano cuprous sulfide. Background Art

[0002] Nanosemiconductor materials exhibit unique optical properties due to quantum size effects and macroscopic quantum tunneling, which give them potential applications in the fields of light and electricity. Cuprous sulfide (Cu2S), a p-type semiconductor with a narrow bandgap (Eg = 1.2-1.24 eV), not only possesses excellent chemical and thermal stability but is also a high-quality optoelectronic material. It has been widely used in various optoelectronic fields, including solar cells, optoelectronic devices, and photocatalysis.

[0003] Currently, liquid-phase thermal synthesis is a common method for preparing nanocuprous sulfide. For example, nanocuprous sulfide powders are synthesized via a high-temperature polyol method using copper acetate as the copper source, thiourea as the sulfur source, and diethylene glycol as the solvent and reducing agent. Alternatively, nanocuprous sulfide powders are prepared via a hydrothermal synthesis method using copper nitrate trihydrate and thiourea as raw materials and thioglycolic acid as a stabilizer. However, these methods present challenges such as complex operation, demanding preparation conditions, and the need for prior preparation of metal-organic precursors. Furthermore, the resulting cuprous sulfide powders are large in size and have a wide particle size distribution, making them difficult to meet the demands of high-precision applications.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The object of the present invention is to provide a preparation method of nano-cuprous sulfide and nano-cuprous sulfide, aiming to solve at least one of the above-mentioned technical problems in the prior art.

[0006] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted: A first aspect of the present invention provides a method for preparing nano-cuprous sulfide. The method comprises adding a sulfur source solution to an acidic complex solution of cuprous ions to obtain an intermediate suspension; then subjecting the intermediate suspension to an ultrasonic reaction, and continuing the reaction for 1 to 2 hours after the system becomes a black suspension. The reaction is then stopped and the system is subjected to solid-liquid separation to obtain a precipitate; and finally, the precipitate is washed and vacuum-dried to obtain nano-cuprous sulfide. The sulfur source in the sulfur source solution comprises a thioamide compound.

[0007] Furthermore, the thioamide compound includes at least one of alkylthioamide, arylthioamide, heteroarylthioamide, N-alkylthioamide, N-arylthioamide and N,N-disubstituted thioamide.

[0008] Preferably, the alkylthioamide includes at least one of thioacetamide, thiopropionamide, and thioisobutyramide.

[0009] Preferably, the arylthioamide comprises thiobenzamide.

[0010] Preferably, the heteroarylthioamide includes 2-pyridinemethanethioamide.

[0011] Preferably, the N-alkylthioamide comprises N-methylthioacetamide.

[0012] Preferably, the N-arylthioamide comprises N-phenylthioacetamide.

[0013] Preferably, the N,N-disubstituted thioamide includes N,N-dimethylthioacetamide.

[0014] Furthermore, the preparation method of the cuprous ion acidic complex solution is as follows: the cleaned cuprous chloride is added to a saturated sodium chloride solution and stirred evenly, and then hydrochloric acid is added and stirred until the cuprous chloride is dissolved to obtain the cuprous ion acidic complex solution.

[0015] Preferably, the amount of the saturated sodium chloride solution is 2 to 5 times the mass of cuprous chloride.

[0016] Preferably, the amount of hydrochloric acid used is 0.5 to 1.0 times the mass of cuprous chloride.

[0017] Preferably, the volume concentration of the hydrochloric acid is 3-8%.

[0018] Preferably, the concentration of cuprous chloride in the acidic complex solution of cuprous ions is 2-3 mol / L.

[0019] Furthermore, the sulfur source solution is an aqueous solution of a sulfur source or an alcohol aqueous solution of a sulfur source.

[0020] Preferably, the temperature of the sulfur source aqueous solution is 40-70°C.

[0021] Preferably, the concentration of the sulfur source aqueous solution is 1-3 mol / L.

[0022] Furthermore, the molar ratio of cuprous ions to the sulfur source is 1:(0.5~1).

[0023] Furthermore, the temperature of the ultrasonic reaction is 90-95° C. and the time is 1-3 h; Preferably, the ultrasonic reaction is carried out under stirring.

[0024] Furthermore, the washing includes washing with pure water and washing with anhydrous ethanol performed in sequence.

[0025] Preferably, the conductivity of the pure water after washing is less than 100 μS / cm.

[0026] Furthermore, the vacuum drying temperature is 60-70° C., the vacuum degree is less than 100 kPa, and the time is 1.5-3 h.

[0027] The second aspect of the present invention provides nano-cuprous sulfide, which is prepared by the preparation method described in the first aspect.

[0028] Furthermore, the D50 of the nano-cuprous sulfide is 100-250 nm.

[0029] Compared with the prior art, the present invention has at least the following beneficial effects: The preparation method provided by the present invention provides an intermediate suspension with excellent stability as a precursor for cuprous sulfide. Ultrasound is used to promote the formation and conversion of the intermediate, effectively controlling the particle size of nano-cuprous sulfide, resulting in a uniform and small distribution with good uniformity and dispersibility. This preparation method also features mild reaction conditions, good reproducibility, and ease of large-scale production.

[0030] The nano-cuprous sulfide provided by the present invention has the advantages of the above-mentioned preparation method, so that the prepared nano-cuprous sulfide has a large specific surface area, high activity, and good dispersibility, thereby improving the performance and application effect of cuprous sulfide in the fields of light, electricity, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0032] Figure 1 This is a preparation method roadmap for Example 1; Figure 2 This is a scanning electron microscope image of the cuprous sulfide nanopowder obtained in Example 1; Figure 3 This is a scanning electron microscope image of the cuprous sulfide nanopowder obtained in Example 1; Figure 4 This is a particle size distribution diagram of the cuprous sulfide nanopowder obtained in Example 1; Figure 5 This is a particle size distribution diagram of the cuprous sulfide nanopowder obtained in Example 2; Figure 6 This is the particle size distribution diagram of the cuprous sulfide nanopowder obtained in Example 3. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0034] Hereinafter, the terms "including", "having" and their cognates, which may be used in various embodiments of the present invention, are intended only to indicate specific features, numbers, steps, operations, elements, components or combinations of the foregoing items, and should not be understood as first excluding the existence of one or more other features, numbers, steps, operations, elements, components or combinations of the foregoing items or the possibility of adding one or more features, numbers, steps, operations, elements, components or combinations of the foregoing items.

[0035] A first aspect of the present invention provides a method for preparing nano-cuprous sulfide. The method comprises adding a sulfur source solution to an acidic complex solution of cuprous ions to obtain an intermediate suspension; then subjecting the intermediate suspension to an ultrasonic reaction, and continuing the reaction for 1 to 2 hours after the system becomes a black suspension. The reaction is then stopped and the system is subjected to solid-liquid separation to obtain a precipitate; and finally, the precipitate is washed and vacuum-dried to obtain nano-cuprous sulfide. The sulfur source in the sulfur source solution comprises a thioamide compound.

[0036] The preparation method provided by the present invention provides an intermediate suspension with excellent stability as a precursor for cuprous sulfide. Ultrasound is used to promote the formation and conversion of the intermediate, effectively controlling the particle size of nano-cuprous sulfide, resulting in a uniform and small distribution with good uniformity and dispersibility. This preparation method also features mild reaction conditions, good reproducibility, and ease of large-scale production.

[0037] Specifically, thioamide compounds act as monodentate ligands, through the lone pair electrons of sulfur atom (S) and Cu + Coordination. Sulfur atom acts as a soft base and reacts with soft acid Cu + (+1 valence) has a higher affinity. Cu + The initial coordination environment is linear ([Cl–Cu–Cl] - ), but after adding thioamide compounds, it may be expanded to tetrahedral or planar tetragonal coordination.

[0038] Taking thioacetamide as an example, the four-coordinate tetrahedral structure: Cu + Center with two Cl - It coordinates with the two S atoms of thioacetamide to form a neutral complex [CuCl2(CH3CSNH2)2]. The charge balance is achieved by Cl -Layered or polymeric structure: Thioacetamide may bridge multiple Cu atoms through S atoms. + center, forming chain or layered polymers, such as [CuCl(CH3CSNH2)] n , where Cl - Alternately coordinate with S to enhance structural stability.

[0039] The alkyl, phenyl, and aryl groups in thioamide compounds provide hydrophobicity, while the large molecular weight or polymeric structure of the complex makes it difficult to dissolve in water, forming colloids or suspensions. At the same time, the surface charge may be generated by Cl - Or the uncoordinated NH2 groups are partially neutralized to reduce aggregation and maintain suspension stability. A stable suspension is conducive to the formation of nano products, and the particle size of the nano products can also be controlled by keeping the concentration of the suspension within a certain range.

[0040] Furthermore, the thioamide compound includes at least one of alkylthioamide, arylthioamide, heteroarylthioamide, N-alkylthioamide, N-arylthioamide and N,N-disubstituted thioamide.

[0041] Preferably, the alkylthioamide includes at least one of thioacetamide, thiopropionamide, and thioisobutyramide.

[0042] Preferably, the arylthioamide comprises thiobenzamide.

[0043] Preferably, the heteroarylthioamide includes 2-pyridinemethanethioamide.

[0044] Preferably, the N-alkylthioamide comprises N-methylthioacetamide.

[0045] Preferably, the N-arylthioamide comprises N-phenylthioacetamide.

[0046] Preferably, the N,N-disubstituted thioamide includes N,N-dimethylthioacetamide.

[0047] Furthermore, the preparation method of the cuprous ion acidic complex solution is as follows: the washed cuprous chloride is added to a saturated sodium chloride solution and stirred evenly, and then hydrochloric acid is added and stirred until the cuprous chloride is dissolved, thereby obtaining the cuprous ion acidic complex solution, i.e., dichlorocopper (I) complex ion ([CuCl2] - ).

[0048] Use hydrochloric acid to wash cuprous chloride 2 to 3 times to remove the high-priced copper in the raw material.

[0049] Preferably, the amount of the saturated sodium chloride solution is 2 to 5 times the mass of cuprous chloride.

[0050] Typically but not limiting, the amount of saturated sodium chloride solution used can be, for example, 2 times, 3 times, 4 times or 5 times the mass of cuprous chloride, or any value within the range of 2 to 5 times.

[0051] Preferably, the amount of hydrochloric acid used is 0.5 to 1.0 times the mass of cuprous chloride.

[0052] Typically but not limitatively, the amount of hydrochloric acid used can be, for example, 0.5 times, 0.6 times, 0.7 times, 0.8 times, 0.9 times or 1.0 times the mass of cuprous chloride, or any value within the range of 0.5 to 1.0 times.

[0053] Preferably, the volume concentration of the hydrochloric acid is 3-8%.

[0054] Preferably, the concentration of cuprous chloride in the acidic complex solution of cuprous ions is 2-3 mol / L.

[0055] Typically but not limitatively, the concentration of cuprous chloride in the acidic complex solution of cuprous ions may be, for example, 2 mol / L, 2.5 mol / L or 3 mol / L, or any value within the range of 2 to 3 mol / L.

[0056] Furthermore, the sulfur source solution is an aqueous sulfur source solution or an alcoholic sulfur source aqueous solution. The alcoholic sulfur source aqueous solution refers to a mixture of an alcohol (such as methanol, ethanol, etc.) and water, in which the thioamide compound is dissolved. In some embodiments of the present invention, the alcohol content of the pure aqueous solution is 10-90 wt%, preferably 50-60 wt%.

[0057] Preferably, the temperature of the sulfur source aqueous solution is 40-60°C.

[0058] Typically but not limitatively, the temperature of the sulfur source aqueous solution may be, for example, 40°C, 45°C, 50°C, 55°C or 60°C, or any value within the range of 40-60°C.

[0059] Preferably, the concentration of the sulfur source aqueous solution is 1-3 mol / L.

[0060] Typically but not limitatively, the concentration of the sulfur source aqueous solution may be, for example, 1 mol / L, 1.5 mol / L, 2 mol / L or 3 mol / L, or any value within the range of 1 to 3 mol / L.

[0061] Furthermore, the molar ratio of cuprous ions to the sulfur source is 1:(0.5~1).

[0062] Typically but not limiting, the molar number of the sulfur source can be half to equal to the molar number of the cuprous ion, for example, 1:0.5, 1:0.75, 1:1, or any ratio within the range of 1:(0.5-1).

[0063] Furthermore, the ultrasonic reaction temperature is 90-95°C for 1-3 hours. Ultrasonic treatment can provide energy, promoting the decomposition of the intermediate and the formation of cuprous sulfide. Under the action of ultrasound, the intermediate decomposes, releasing sulfur atoms, which combine with cuprous ions to form cuprous sulfide. Ultrasonic treatment can also prevent particle agglomeration, helping to form uniform nanoparticles.

[0064] Typically but not limitatively, the temperature of the ultrasonic reaction can be, for example, 90°C, 92°C, 93°C, 94°C or 95°C, or any value within the range of 90-95°C; the time is 1 hour, 1.5 hours, 2 hours or 3 hours, or any value within the range of 1-3 hours.

[0065] Preferably, the ultrasonic reaction is carried out under stirring to ensure the uniformity of the reaction and prevent the cuprous sulfide particles from agglomerating and increasing in particle size.

[0066] Furthermore, the washing includes washing with pure water and washing with anhydrous ethanol performed in sequence.

[0067] Preferably, the conductivity of the pure water after washing is less than 100 μS / cm, which can effectively remove anionic or cationic impurities on the surface of the nanoparticles and prevent agglomeration of the nanoparticles caused by impurity ions.

[0068] Furthermore, the vacuum drying temperature is 60-70° C., the vacuum degree is less than 100 kPa, and the time is 1.5-3 h.

[0069] Typically but not limitatively, the temperature during the vacuum drying process can be 60°C, 65°C or 70°C, or any temperature value within the range of 60-70°C; the vacuum degree can be less than 100 kPa, and the specific value can be 90 kPa, 95 kPa or other values ​​lower than 100 kPa; the drying time can be 1.5 hours, 2 hours, 2.5 hours or 3 hours, or any time value within the range of 1.5-3 hours.

[0070] The second aspect of the present invention provides nano-cuprous sulfide, which is prepared by the preparation method described in the first aspect.

[0071] The nano-cuprous sulfide provided by the present invention has the advantages of the above-mentioned preparation method, so that the prepared nano-cuprous sulfide has a large specific surface area, high activity, and good dispersibility, thereby improving the performance and application effect of cuprous sulfide in the fields of light, electricity, etc.

[0072] Furthermore, the D50 of the nano-cuprous sulfide is 100-250 nm.

[0073] The present invention is further illustrated below by specific examples and comparative examples. However, it should be understood that these examples are merely for the purpose of further explanation and should not be construed as limiting the present invention in any form. The raw materials used in the examples and comparative examples of the present invention, unless otherwise specified, were prepared under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used without manufacturer's indication are all commercially available conventional products.

[0074] Example 1 This embodiment provides a nano-cuprous sulfide, the preparation method of which is as follows Figure 1 As shown, the details are as follows: 1. Wash 60 g (0.61 mol) of cuprous chloride twice with dilute hydrochloric acid (4.76% by volume). Add the washed cuprous chloride to 200 mL of saturated sodium chloride solution. Add 30 mL of hydrochloric acid while stirring. Continue stirring until the cuprous chloride is completely dissolved. Filter to form a light brown solution, obtaining an acidic complex solution of cuprous ions. Dissolve 24 g (0.32 mol) of thioacetamide in 150 mL of 50°C pure water and filter to obtain a thioacetamide solution.

[0075] 2. Slowly add the thioacetamide solution to the acidic complex solution of cuprous ions under stirring to form a light yellow suspension. Stir at room temperature for 20 minutes to mix the two solutions evenly. Place the mixed solution in an ultrasonic stirring reactor, heat to 90°C and stir for 3 hours. The color gradually changes from light yellow to brown-black to black. Cool to 85°C and continue stirring for 2 hours to stabilize the generated nanoparticles. Turn off the ultrasonic stirring reactor. Let it stand, separate the lower precipitate, wash with water and test the conductivity to be 86μS / cm. Then wash once with anhydrous ethanol. Vacuum dry the filter cake at 60°C and vacuum degree 95kPa for 2 hours to obtain cuprous sulfide nanopowder.

[0076] Example 2 This embodiment provides a nano-cuprous sulfide, the preparation method of which is as follows: 1. Wash 60 g (0.61 mol) of cuprous chloride twice with dilute hydrochloric acid (4.76% by volume). Add 150 mL of saturated sodium chloride solution to the washed cuprous chloride. Add 40 mL of hydrochloric acid while stirring. Continue stirring until the cuprous chloride is completely dissolved. Filter to form a light brown solution, obtaining an acidic complex solution of cuprous ions. Dissolve 24 g (0.32 mol) of thioacetamide in 120 mL of 70°C pure water and filter to obtain a thioacetamide solution.

[0077] 2. Slowly add the thioacetamide solution to the acidic complex solution of cuprous ions under stirring to form a light yellow suspension. Stir at room temperature for 20 minutes to mix the two solutions evenly. Place the mixed solution in an ultrasonic stirring reactor, heat to 90°C and stir for 3 hours, and the color gradually changes from light yellow to brown-black to black. Cool to 85°C and continue stirring for 2 hours, then turn off the ultrasonic stirring reactor. Let stand to separate the lower precipitate, and the conductivity of the water washing test is 59μS / cm. Then wash once with anhydrous ethanol, and vacuum dry the filter cake at 70°C and 95kPa for 3 hours to obtain cuprous sulfide nanopowder.

[0078] Example 3 This embodiment provides a nano-cuprous sulfide, the preparation method of which is as follows: 1. Wash 600g (6.06mol) of cuprous chloride twice with dilute hydrochloric acid (4.76% by volume). Add 1500mL of saturated sodium chloride solution to the washed cuprous chloride. Add 400mL of hydrochloric acid while stirring. Continue stirring until the cuprous chloride is completely dissolved. Filter to form a light brown solution, obtaining an acidic complex solution of cuprous ions. Dissolve 240g (3.19mol) of thioacetamide in 1500mL of 60°C pure water and filter to obtain a thioacetamide solution.

[0079] 2. Slowly add the thioacetamide solution to the acidic complex solution of cuprous ions under stirring to form a light yellow suspension. Stir at room temperature for 20 minutes to mix the two solutions evenly. Place the mixed solution in an ultrasonic stirring reactor, heat to 95°C and stir for 3 hours. The color gradually changes from light yellow to brown-black to black. Cool to 80°C and continue stirring for 2 hours. Turn off the ultrasonic stirring reactor. Let it stand and separate the lower precipitate. The conductivity of the washed solution is 92μS / cm. Then wash it once with anhydrous ethanol. The filter cake is vacuum dried at 60°C and 95kPa for 2 hours to obtain cuprous sulfide nanopowder.

[0080] Example 4 This embodiment provides a nano-cuprous sulfide. The difference from Example 1 is that 28.53 g (0.32 mol) of thiopropionamide is used instead of thioacetamide, and the solvent is replaced by an equal volume of 55 wt% ethanol aqueous solution. The remaining steps are the same as those in Example 1 and are not repeated here.

[0081] Example 5 This embodiment provides a nano-cuprous sulfide. The difference from Example 1 is that 32.84 g (0.32 mol) of thioisobutyramide is used instead of thioacetamide, and the solvent is replaced by an equal volume of 55 wt% ethanol aqueous solution. The remaining steps are the same as those in Example 1 and are not repeated here.

[0082] Example 6 This embodiment provides a nano-cuprous sulfide. The difference from Example 1 is that 47.76 g (0.32 mol) of thiobenzamide is used instead of thioacetamide, and the solvent is replaced by an equal volume of 55 wt% ethanol aqueous solution. The remaining steps are the same as those in Example 1 and are not repeated here.

[0083] Example 7 This embodiment provides a nano-cuprous sulfide. The difference from Example 1 is that 43.05 g (0.32 mol) of 2-pyridinemethylthioamide is used instead of thioacetamide, and the solvent is replaced by an equal volume of 55 wt% ethanol aqueous solution. The remaining steps are the same as those in Example 1 and are not repeated here.

[0084] Example 8 This embodiment provides a nano-cuprous sulfide. The difference from Example 1 is that 27.90 g (0.32 mol) of N-methylthioacetamide is used instead of thioacetamide, and the solvent is replaced by an equal volume of 55 wt% ethanol aqueous solution. The remaining steps are the same as those in Example 1 and are not repeated here.

[0085] Example 9 This embodiment provides a nano-cuprous sulfide. The difference from Example 1 is that 31.11 g (0.32 mol) of N,N-dimethylthioacetamide is used instead of thioacetamide, and the solvent is replaced by an equal volume of 90 wt% ethanol aqueous solution. The remaining steps are the same as those in Example 1 and are not repeated here.

[0086] Example 10 This embodiment provides a nano-cuprous sulfide. The difference from Example 1 is that 12 g (0.16 mol) of thioacetamide and 23.88 g (0.16 mol) of thiobenzamide are used instead of thioacetamide, and the solvent is replaced by an equal volume of 55 wt% ethanol aqueous solution. The remaining steps are the same as those in Example 1 and are not repeated here.

[0087] Characteristic example The cuprous sulfide nanopowder obtained in Example 1 was subjected to a scanning electron microscope, and the obtained SEM image is as follows: Figure 2 and Figure 3 shown.

[0088] from Figure 2 and Figure 3 It can be seen that the cuprous sulfide particles are in the form of irregular polyhedrons, with uniform particle size and good dispersion between the particles.

[0089] Results The cuprous sulfide powders obtained in the examples and comparative examples were tested by dynamic light scattering (DLS), and the obtained data are recorded in Table 1.

[0090] Table 1

[0091] The DLS results of Examples 1-3 were plotted to obtain a particle size distribution diagram, corresponding to Figure 4 、 Figure 5 and Figure 6 shown.

[0092] As can be seen from Table 1, different sulfur sources can stably prepare nano-cuprous sulfide, and under the same process conditions, the particle size range is relatively stable and the repeatability is good. Figure 4 、 Figure 5 、 Figure 6 It can be seen that the particle size distribution graph presents a symmetrical bell-shaped curve, the mean and peak positions basically coincide, and the data dispersion is small. The Gaussian fitting verification shows that the measured distribution has a high degree of agreement with the normal distribution theoretical curve (R 2 >0.85), which is consistent with the normal distribution law.

[0093] Finally, it should be noted that the above-described embodiments are only specific implementations of the present invention, which are used to illustrate the technical solutions of the present invention, rather than to limit them. The scope of protection of the present invention is not limited thereto. Although the present invention has been described in detail with reference to the above-described embodiments, those skilled in the art should understand that any person skilled in the art can modify or easily conceive of changes to the technical solutions described in the above-described embodiments within the technical scope disclosed by the present invention, or replace some of the technical features therein with equivalents. Such modifications, changes, or replacements do not deviate from the spirit and scope of the technical solutions of the embodiments of the present invention, and should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for preparing nano-cuprous sulfide, characterized in that: A sulfur source solution is added to the acidic complex solution of cuprous ions to obtain an intermediate suspension; the intermediate suspension is then subjected to ultrasonic reaction, and the system becomes a black suspension and the reaction is continued for 1 to 2 hours, and then the reaction is stopped and the system is subjected to solid-liquid separation to obtain a precipitate; finally, the precipitate is washed and vacuum dried to obtain nano-cuprous sulfide; Wherein, the sulfur source in the sulfur source solution includes thioamide compounds.

2. The preparation method according to claim 1, characterized in that The thioamide compound includes at least one of alkylthioamide, arylthioamide, heteroarylthioamide, N-alkylthioamide, N-arylthioamide and N,N-disubstituted thioamide; Preferably, the alkylthioamide includes at least one of thioacetamide, thiopropionamide, and thioisobutyramide; Preferably, the arylthioamide comprises thiobenzamide; Preferably, the heteroarylthioamide comprises 2-pyridinemethanethioamide; Preferably, the N-alkylthioamide comprises N-methylthioacetamide; Preferably, the N-arylthioamide comprises N-phenylthioacetamide; Preferably, the N,N-disubstituted thioamide includes N,N-dimethylthioacetamide.

3. The preparation method according to claim 1, characterized in that The preparation method of the cuprous ion acidic complex solution is as follows: the cleaned cuprous chloride is added to a saturated sodium chloride solution and stirred evenly, and then hydrochloric acid is added and stirred until the cuprous chloride is dissolved, thereby obtaining the cuprous ion acidic complex solution; Preferably, the amount of the saturated sodium chloride solution is 2 to 5 times the mass of cuprous chloride; Preferably, the amount of hydrochloric acid used is 0.5 to 1.0 times the mass of cuprous chloride; Preferably, the volume concentration of the hydrochloric acid is 3-8%; Preferably, the concentration of cuprous chloride in the acidic complex solution of cuprous ions is 2-3 mol / L.

4. The preparation method according to claim 1, characterized in that The sulfur source solution is an aqueous solution of a sulfur source or an alcohol aqueous solution of a sulfur source; Preferably, the temperature of the aqueous solution of the sulfur source is 40-70°C; Preferably, the concentration of the aqueous solution of the sulfur source is 1-3 mol / L.

5. The preparation method according to claim 3 or 4, characterized in that The molar ratio of cuprous ion to sulfur source is 1:(0.5~1).

6. The preparation method according to any one of claims 1 to 4, characterized in that The temperature of the ultrasonic reaction is 90-95°C and the time is 1-3 hours; Preferably, the ultrasonic reaction is carried out under stirring.

7. The preparation method according to any one of claims 1 to 4, characterized in that The washing comprises washing with pure water and washing with anhydrous ethanol, which are carried out in sequence; Preferably, the conductivity of the pure water after washing is less than 100 μS / cm.

8. The preparation method according to any one of claims 1 to 4, characterized in that The vacuum drying temperature is 60-70° C., the vacuum degree is less than 100 kPa, and the time is 1.5-3 hours.

9. A nano-cuprous sulfide, characterized in that: The preparation method according to any one of claims 1 to 8 is used to prepare the compound.

10. The nano-cuprous sulfide according to claim 9, characterized in that: D50 is 100~250nm.

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