Superfine cuprous oxide as well as preparation method and application thereof

Abstract

The invention relates to superfine cuprous oxide and a preparation method and application thereof, and the preparation method comprises the following steps: carrying out first mixing on a copper salt mixed solution and a precipitant solution to obtain a copper hydroxide suspension; wherein the copper salt mixed solution comprises copper salt, aluminum salt and a solvent; and carrying out second mixing on the copper hydroxide suspension and a reducing agent solution to obtain the superfine cuprous oxide. According to the invention, a liquid phase precipitation method is matched with aluminum salt as a nucleation inducer, so that the particle size of cuprous oxide particles can be refined, and the superfine cuprous oxide with high sphericity, high stability, uniform morphology, narrower particle size distribution and uniform size is obtained; the liquid phase precipitation method adopted by the invention does not need harsh reaction conditions, and is simple in equipment, convenient to operate, easy in condition control and suitable for large-scale production, and the aluminum salt is wide in source and low in price, so that the superfine cuprous oxide with relatively excellent performance can be prepared at relatively low cost, the preparation requirements of the method are met, and the method has good economic benefits.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of inorganic materials, and in particular to ultrafine cuprous oxide and a preparation method and application thereof. Background Art

[0002] Cuprous oxide (Cu2O) is an important p-type semiconductor material with great application potential in the fields of photoelectric catalysis, solar cells, sensors and antibacterial materials. Its performance is largely determined by its morphology, size and crystallinity. Ultrafine cuprous oxide, especially nano-sized cuprous oxide, often exhibits better physical and chemical properties than ordinary cuprous oxide due to its small size effect, surface effect and quantum confinement effect.

[0003] At present, the methods for preparing ultrafine cuprous oxide mainly include chemical reduction, hydrothermal method or electrochemical method. However, these methods generally have some problems such as complex process, long time, high cost or low yield. Some methods also need to meet high temperature and high pressure conditions or use expensive surfactants, which also increases the cost of preparation. In addition, the morphology and size of the product have a great influence on the performance of ultrafine cuprous oxide, and the morphology and size are relatively difficult to control, which will also affect the performance and preparation of ultrafine cuprous oxide.

[0004] CN103435089A discloses a rough-surfaced spherical cuprous oxide micro-nano particle and a preparation method thereof, wherein an inorganic copper salt is dissolved in a solvent, and then ethylenediaminetetraacetic acid is added, and ultrasonic dissolution is performed to obtain a clear solution, and then a reducing agent is added, and the temperature is controlled at 130-160°C for hydrothermal reaction for 2-6 hours, and the obtained reaction solution is centrifuged at a speed of 6000-8000r / min, and the precipitate is washed until the pH of the eluate is neutral, and then the temperature is controlled at 40-80°C for drying to obtain a rough-surfaced spherical cuprous oxide micro-nano particle. Although the above process also prepares spherical micro-nano particle cuprous oxide, it is still doped with other short rod-shaped powders, and the size of the micro-nano particles is uneven.

[0005] CN104261457A discloses a method for preparing cuprous oxide particles with controllable morphology and size, which includes: after mixing a copper sulfate solution and PVP, successively adding a sodium citrate solution and a sodium carbonate solution, adjusting the pH value of the solution to be greater than 7, standing and then adding a glucose solution, and heating in a constant temperature water bath to obtain a suspension of cuprous oxide, and obtaining micro-nano cuprous oxide spherical particles through post-treatment. However, in the above preparation process, it is necessary to strictly control the reaction conditions within the corresponding range to prepare the corresponding spherical cuprous oxide particles, and in the obtained spherical powder, it is still inevitable that there are particles with other morphologies, such as cubes, polyhedrons, and hexahedrons, etc., and it is impossible to ensure that all powders have a spherical morphology. There are many uncertain factors in the reaction process, the reaction conditions are harsh, and the surfactant used will further increase the preparation cost.

[0006] Therefore, the present invention aims to overcome the deficiencies of the prior art, provide a method for preparing ultrafine cuprous oxide with simple operation, mild conditions, low cost, environmental friendliness and easy industrial production, and realize effective regulation of the morphology, size and crystallinity of ultrafine cuprous oxide, laying a foundation for its applications in the fields of photoelectrocatalysis, solar cells, sensors and antibacterial materials, etc., which has important significance. Summary of the Invention

[0007] To solve the above technical problems, the present invention provides an ultrafine cuprous oxide and its preparation method and application. The present invention uses the liquid-phase precipitation method in combination with an aluminum salt as a nucleation inducer, which can refine the particle size of cuprous oxide particles, and then obtain ultrafine cuprous oxide with high sphericity, high stability, uniform morphology, narrow particle size distribution and uniform size; and the liquid-phase precipitation method adopted by the present invention does not require harsh reaction conditions, has simple equipment, convenient operation, easy control of conditions, is suitable for large-scale production, and the aluminum salt has a wide source and low price. Furthermore, it can realize the preparation of ultrafine cuprous oxide with better performance at a lower cost, meet the preparation requirements of the present invention, and has good economic benefits.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a method for preparing ultrafine cuprous oxide, and the preparation method includes the following steps:

[0010] (1) Perform a first mixing of a copper salt mixed solution and a precipitant solution to obtain a cupric hydroxide suspension;

[0011] Wherein, the copper salt mixed solution includes a copper salt, an aluminum salt and a solvent;

[0012] (2) Perform a second mixing of the cupric hydroxide suspension obtained in step (1) and a reducing agent solution to obtain ultrafine cuprous oxide.

[0013] In the present invention, an aluminum salt is additionally added to the reaction raw materials as a nucleation inducer. During the subsequent addition of the precipitant and the reaction process, as the pH value of the reaction mixture increases, aluminum hydroxide (K sp is approximately 1.3×10 -33 ) will precipitate prior to copper hydroxide (K sp is approximately 2.2×10 -20 ). Therefore, the initially formed aluminum hydroxide will serve as crystal seeds to promote the crystallization of copper hydroxide, refine its crystal grains, and further refine the crystal grains of cuprous oxide obtained by subsequent reduction, forming ultrafine cuprous oxide. At the same time, since aluminum hydroxide will dissolve under alkaline conditions, there will be basically no aluminum impurities in the cuprous oxide particles obtained after reduction. In summary, the addition of the aluminum salt to the reaction raw materials can achieve the effect of refining the particle size of cuprous oxide particles, and further obtain ultrafine cuprous oxide with high sphericity, high stability, uniform morphology, narrow particle size distribution, and uniform size. In addition, the liquid-phase precipitation method adopted in the present invention does not require harsh reaction conditions, has simple equipment, convenient operation, easy control of conditions, is suitable for large-scale production, and the aluminum salt has a wide source and low price. Therefore, it can realize the preparation of ultrafine cuprous oxide with excellent performance at a relatively low cost, meet the preparation requirements of the present invention, and has good economic benefits.

[0014] As a preferred technical solution of the present invention, in the copper salt mixed solution in step (1), the concentration of aluminum ions is 0.002 mol / L to 0.1 mol / L, such as 0.002 mol / L, 0.003 mol / L, 0.004 mol / L, 0.005 mol / L, 0.006 mol / L, 0.007 mol / L, 0.008 mol / L, 0.009 mol / L, 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L or 0.1 mol / L, etc., and preferably 0.01 mol / L to 0.05 mol / L.

[0015] In the present invention, regulating the concentration of aluminum ions to 0.002 mol / L to 0.1 mol / L can refine the particle size of cuprous oxide particles. Further, regulating to 0.01 mol / L to 0.05 mol / L can take into account obvious grain refinement, purity, and impurity element content within a more optimal range, and the obtained ultrafine cuprous oxide has better performance and is more suitable for applications in different scenarios. If the concentration of aluminum ions is too high, the aluminum impurity content in cuprous oxide will increase, affecting the purity of cuprous oxide; if the concentration of aluminum ions is too low, the effect of grain refinement is not obvious.

[0016] Preferably, in the copper salt mixed solution in step (1), the concentration of copper ions is 0.1 mol / L to 1.26 mol / L, such as 0.1 mol / L, 0.3 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, 1.2 mol / L or 1.26 mol / L, etc., and preferably 0.5 mol / L to 1 mol / L.

[0017] As a preferred technical solution of the present invention, the molar ratio of the precipitant in the precipitant solution in step (1) to the copper ions is (2.5 to 4):1, such as 2.5:1, 2.8:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1 or 4:1, etc., and preferably (3 to 3.5):1.

[0018] Preferably, the concentration of the precipitant solution in step (1) is 9 mol / L to 12 mol / L, such as 9 mol / L, 9.5 mol / L, 10 mol / L, 10.5 mol / L, 11 mol / L, 11.5 mol / L or 12 mol / L, etc.

[0019] As a preferred technical solution of the present invention, the molar ratio of the reducing agent in the reducing agent solution in step (2) to the copper in the copper hydroxide suspension is (0.5 to 1.5):1, such as 0.5:1, 0.6:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.2:1 or 1.5:1, etc., and preferably (0.75 to 1):1.

[0020] Preferably, the concentration of the reducing agent solution in step (2) is 500 g / L to 1000 g / L, such as 500 g / L, 600 g / L, 700 g / L, 800 g / L, 900 g / L or 1000 g / L, etc., and preferably 700 g / L to 900 g / L.

[0021] As a preferred technical solution of the present invention, the temperature of the second mixing in step (2) is 40°C to 70°C, such as 40°C, 45°C, 50°C, 55°C, 60°C, 65°C or 70°C, etc., and preferably 55°C to 65°C.

[0022] As a preferred technical solution of the present invention, the precipitant solution in step (1) includes sodium hydroxide solution and / or potassium hydroxide solution.

[0023] Preferably, in the copper salt mixed solution in step (1), the types of the copper salt and the aluminum salt independently include sulfate and / or chloride.

[0024] Preferably, in the copper salt mixed solution in step (1), the solvent includes deionized water.

[0025] Preferably, the reducing agent solution in step (2) includes a glucose solution.

[0026] Preferably, the first mixing in step (1) is carried out at room temperature.

[0027] It should be noted that the "room temperature" in the present invention refers to 25°C ± 5°C.

[0028] Preferably, the first mixing in step (1) and the second mixing in step (2) each independently include stirring.

[0029] It should be noted that in the present invention, there are no specific requirements and special limitations on the stirring speed in the first mixing in step (1) and the second mixing in step (2), as long as the stirring is uniform. Those skilled in the art can make adaptive selections and adjustments according to the actual situation.

[0030] Preferably, after the second mixing in step (2), it further includes the steps of solid-liquid separation, washing, and drying of the obtained reaction solid particles.

[0031] It should be noted that in the present invention, there are no specific requirements and special limitations on the methods of solid-liquid separation, washing, and drying and the specific parameters of the selected methods. As long as the methods and parameters commonly used by those skilled in the art are applicable to the present invention, those skilled in the art can make adaptive selections and adjustments according to the actual situation.

[0032] As a preferred technical solution of the present invention, the preparation method includes the following steps:

[0033] (1) First mix a copper salt mixed solution and a precipitant solution at room temperature, stir evenly to obtain a copper hydroxide suspension;

[0034] Among them, the copper salt mixed solution includes a copper salt, an aluminum salt, and a solvent; in the copper salt mixed solution, the concentration of aluminum ions is 0.002 mol / L to 0.1 mol / L, and the concentration of copper ions is 0.1 mol / L to 1.26 mol / L; the molar ratio of the precipitant in the precipitant solution to the copper ions is (2.5 to 4):1; the concentration of the precipitant solution is 9 mol / L to 12 mol / L;

[0035] (2) Second mix the copper hydroxide suspension obtained in step (1) and a reducing agent solution at 40°C to 70°C, carry out the reaction while maintaining the temperature and stirring conditions, and carry out solid-liquid separation, washing, and drying of the obtained reaction solid particles to obtain ultrafine cuprous oxide;

[0036] Among them, the molar ratio of the reducing agent in the reducing agent solution to the copper element in the copper hydroxide suspension is (0.5-1.5):1; the concentration of the reducing agent solution is 500 g / L-1000 g / L.

[0037] In a second aspect, the present invention also provides an ultrafine cuprous oxide, which is prepared according to the preparation method described in the first aspect.

[0038] As a preferred technical solution of the present invention, the average particle size D50 of the ultrafine cuprous oxide is 500 nm-1200 nm, such as 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm or 1200 nm, etc.

[0039] In a third aspect, the present invention also provides an application of the ultrafine cuprous oxide. The ultrafine cuprous oxide prepared according to the preparation method described in the first aspect, or the ultrafine cuprous oxide described in the second aspect, is applied to photoelectrocatalysis, solar cells, sensors or antibacterial materials.

[0040] Compared with the prior art, the present invention has at least the following beneficial effects:

[0041] 1) The present invention uses the liquid phase precipitation method in combination with an aluminum salt as a nucleation inducer, which can refine the particle size of cuprous oxide particles, and then obtain ultrafine cuprous oxide. The obtained ultrafine cuprous oxide has a high sphericity, high stability, uniform morphology, narrow particle size distribution and uniform size. The average particle size D50 is 500 nm-1200 nm, the purity is >97%, and the aluminum content of impurity elements is 0.0133% or less.

[0042] 2) The present invention is prepared by the liquid phase precipitation method, which does not require harsh reaction conditions, has simple equipment, convenient operation, easy control of conditions, is suitable for large-scale production, and the aluminum salt has a wide source and low price. It can prepare ultrafine cuprous oxide with better performance at a lower cost, meet the preparation requirements of the present invention, and has good economic benefits. Description of the Drawings

[0043] Figure 1 It is the SEM image of the ultrafine cuprous oxide provided in Example 1 of the present invention.

[0044] Figure 2 It is the SEM image of the ultrafine cuprous oxide provided in Example 2 of the present invention.

[0045] Figure 3 It is the SEM image of the ultrafine cuprous oxide provided in Example 3 of the present invention.

[0046] Figure 4It is the SEM image of cuprous oxide provided by Comparative Example 1 of the present invention. Detailed Embodiments

[0047] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific embodiments. However, the following examples are merely simple examples of the present invention and do not represent or limit the scope of the protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0048] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

[0049] Example 1

[0050] This example provides a method for preparing ultrafine cuprous oxide. The preparation method includes the following steps:

[0051] (1) 1 mol of CuSO4 and 0.025 mol of Al2(SO4)3 are configured into 1 L of a mixed solution (the solvent is deionized water), and mixed evenly with 278 mL of a sodium hydroxide solution with a concentration of 10.8 mol / L at a stirring speed of 300 rpm at room temperature. Continue stirring and reacting to obtain a uniform cupric hydroxide suspension;

[0052] (2) The cupric hydroxide suspension and 200 mL of a glucose solution with a concentration of 810 g / L are heated to 60 °C together. The above glucose solution is added to the cupric hydroxide suspension at one time at a stirring speed of 300 rpm, and continue stirring and reacting at 60 °C and 300 rpm. After the solid particles in the reaction solution turn completely red or orange-yellow, carry out centrifugal separation, wash five times with five times of pure water, and then vacuum dry at 80 °C to obtain ultrafine cuprous oxide.

[0053] Figure 1 The SEM image of the ultrafine cuprous oxide provided by Example 1 of the present invention is shown. It can be seen from the figure that the prepared cuprous oxide has a uniform morphology, a narrow particle size distribution, and a high sphericity.

[0054] Example 2

[0055] This example provides a method for preparing ultrafine cuprous oxide. The preparation method includes the following steps:

[0056] (1) 1 mol of CuSO4 and 0.01 mol of Al2(SO4)3 are configured into 1 L of a mixed solution (the solvent is deionized water), and mixed evenly with 278 mL of a sodium hydroxide solution with a concentration of 10.8 mol / L at a stirring speed of 300 rpm at room temperature. Continue stirring and reacting to obtain a uniform cupric hydroxide suspension;

[0057] (2) Heat the copper hydroxide suspension and 200 mL of glucose solution with a concentration of 810 g / L to 60 °C. Add the above glucose solution to the copper hydroxide suspension at one time under a stirring speed of 300 rpm. Continue stirring and reacting at 60 °C and 300 rpm. After the solid particles in the reaction solution turn completely red or orange-yellow, perform centrifugal separation, wash five times with five times the volume of pure water, and then vacuum dry at 80 °C to obtain ultrafine cuprous oxide.

[0058] Figure 2 Figure 4 shows the SEM image of the ultrafine cuprous oxide provided in Example 2 of the present invention. As can be seen from the figure, the prepared cuprous oxide has a uniform morphology, a narrow particle size distribution, and a high sphericity.

[0059] Example 3

[0060] This example provides a method for preparing ultrafine cuprous oxide, and the preparation method includes the following steps:

[0061] (1) Prepare a 1 L mixed solution (with deionized water as the solvent) by mixing 1 mol of CuSO4 and 0.005 mol of Al2(SO4)3. Mix it evenly with 278 mL of sodium hydroxide solution with a concentration of 10.8 mol / L at a stirring speed of 300 rpm at room temperature, and continue stirring and reacting to obtain a uniform copper hydroxide suspension;

[0062] (2) Heat the copper hydroxide suspension and 200 mL of glucose solution with a concentration of 810 g / L to 60 °C. Add the above glucose solution to the copper hydroxide suspension at one time under a stirring speed of 300 rpm. Continue stirring and reacting at 60 °C and 300 rpm. After the solid particles in the reaction solution turn completely red or orange-yellow, perform centrifugal separation, wash five times with five times the volume of pure water, and then vacuum dry at 80 °C to obtain ultrafine cuprous oxide.

[0063] Figure 3 Figure 5 shows the SEM image of the ultrafine cuprous oxide provided in Example 3 of the present invention. As can be seen from the figure, the prepared cuprous oxide has a uniform morphology, a narrow particle size distribution, and a high sphericity.

[0064] Example 4

[0065] This example provides a method for preparing ultrafine cuprous oxide, and the preparation method includes the following steps:

[0066] (1) Prepare a 1 L mixed solution (with deionized water as the solvent) by mixing 1 mol of CuSO4 and 0.001 mol of Al2(SO4)3. Mix it evenly with 320 mL of sodium hydroxide solution with a concentration of 10.8 mol / L at a stirring speed of 300 rpm at room temperature, and continue stirring and reacting to obtain a uniform copper hydroxide suspension;

[0067] (2) Heat the copper hydroxide suspension and 170 mL of a glucose solution with a concentration of 810 g / L to 40 °C. Add the above glucose solution to the copper hydroxide suspension at one time under a stirring speed of 300 rpm. Continue stirring and reacting at 40 °C and 300 rpm. After the solid particles in the reaction solution turn completely red or orange-yellow, perform centrifugal separation, wash five times with five times the volume of pure water, and then dry in vacuum at 80 °C to obtain ultrafine cuprous oxide.

[0068] Example 5

[0069] This example provides a method for preparing ultrafine cuprous oxide, and the preparation method includes the following steps:

[0070] (1) Prepare a 1 L mixed solution (with deionized water as the solvent) by mixing 1 mol of CuSO4 and 0.05 mol of Al2(SO4)3. Mix it evenly with 278 mL of a sodium hydroxide solution with a concentration of 10.8 mol / L at a stirring speed of 300 rpm at room temperature, and continue stirring and reacting to obtain a uniform copper hydroxide suspension;

[0071] (2) Heat the copper hydroxide suspension and 220 mL of a glucose solution with a concentration of 810 g / L to 70 °C. Add the above glucose solution to the copper hydroxide suspension at one time under a stirring speed of 300 rpm. Continue stirring and reacting at 70 °C and 300 rpm. After the solid particles in the reaction solution turn completely red or orange-yellow, perform centrifugal separation, wash five times with five times the volume of pure water, and then dry in vacuum at 80 °C to obtain ultrafine cuprous oxide.

[0072] Example 6

[0073] This example provides a method for preparing ultrafine cuprous oxide. The difference between this preparation method and that of Example 1 is that the amount of Al2(SO4)3 is 0.2 mol, and the rest of the preparation methods and parameters are the same as those of Example 1.

[0074] Example 7

[0075] This example provides a method for preparing ultrafine cuprous oxide. The difference between this preparation method and that of Example 1 is that the amount of Al2(SO4)3 is 0.003 mol, and the rest of the preparation methods and parameters are the same as those of Example 1.

[0076] Example 8

[0077] This example provides a method for preparing ultrafine cuprous oxide. The difference between this preparation method and that of Example 1 is that the amount of Al2(SO4)3 is 0.04 mol, and the rest of the preparation methods and parameters are the same as those of Example 1.

[0078] Comparative Example 1

[0079] This comparative example provides a method for preparing cuprous oxide, and the preparation method includes the following steps:

[0080] (1) 1 mol of CuSO4 was configured into 1 L of a mixed solution (the solvent was deionized water), and mixed uniformly with 278 mL of a sodium hydroxide solution with a concentration of 10.8 mol / L at a stirring speed of 300 rpm at room temperature, and the stirring reaction was continued to obtain a uniform cupric hydroxide suspension;

[0081] (2) The cupric hydroxide suspension and 200 mL of a glucose solution with a concentration of 810 g / L were heated to 60 °C together. The above glucose solution was added to the cupric hydroxide suspension at one time at a stirring speed of 300 rpm, and the stirring reaction was continued at 60 °C and 300 rpm. After the solid particles in the reaction solution turned completely red or orange-yellow, centrifugal separation was carried out. After washing five times with five times of pure water, vacuum drying was carried out at 80 °C to obtain cuprous oxide.

[0082] Figure 4 The SEM image of the cuprous oxide provided by Comparative Example 1 of the present invention is shown. As can be seen from the figure, the prepared cuprous oxide has a uniform morphology and a high sphericity, but the particle size of the cuprous oxide is relatively large.

[0083] Comparative Example 2

[0084] This comparative example provides a method for preparing cuprous oxide. The difference between the preparation method and Example 1 is that the aluminum salt is replaced with an iron salt. In step (1), 1 mol of CuSO4 and 0.05 mol of FeSO4 were configured into 1 L of a mixed solution (the solvent was deionized water), and the remaining preparation methods and parameters were the same as those in Example 1.

[0085] Comparative Example 3

[0086] This comparative example provides a method for preparing cuprous oxide. The difference between the preparation method and Example 1 is that the aluminum salt is replaced with a zinc salt. In step (1), 1 mol of CuSO4 and 0.05 mol of ZnSO4 were configured into 1 L of a mixed solution (the solvent was deionized water), and the remaining preparation methods and parameters were the same as those in Example 1.

[0087] The average particle size D50 (laser diffraction particle size analyzer, Malvern 3000), purity (HG / T 2961-2010 industrial cuprous oxide standard), and impurity element content (tested by ICP-MS) of the ultrafine cuprous oxide prepared in Examples 1-8 and the cuprous oxide prepared in Comparative Examples 1-3 were tested respectively. The specific test data are shown in Table 1.

[0088] Table 1

[0089] Item Particle Size (nm) Purity (%) Impurity Element Content (%) Example 1 500 97.5 Aluminum 0.0075 Example 2 600 97.6 Aluminum 0.0092 Example 3 800 98.1 Aluminum 0.0069 Example 4 1100 98.2 Aluminum 0.0051 Example 5 700 97.2 Aluminum 0.0133 Example 6 600 95.1 Aluminum 0.5561 Example 7 1200 98.5 Aluminum 0.0023 Example 8 500 97.2 Aluminum 0.0096 Comparative Example 1 1500 97.5 0.0001 (Lower Limit of Impurity Element Detection) Comparative Example 2 3000 95.4 Iron 0.1501 Comparative Example 3 1500 96.3 Zinc 0.0191

[0090] It can be seen from the test results that:

[0091] (1) It can be seen from Examples 1-5, 7-8 that the present invention uses the liquid phase precipitation method in combination with an aluminum salt as a nucleation inducer, and regulates the concentration of the aluminum salt, which can refine the particle size of cuprous oxide particles, and then obtain ultrafine cuprous oxide. Moreover, the corresponding ultrafine cuprous oxide has a high sphericity, high stability, uniform morphology, narrow particle size distribution, uniform size, the average particle size D50 is between 500 nm and 1200 nm, the purity is >97%, and the aluminum content of impurity elements is 0.0133% or less.

[0092] Furthermore, it can be seen from Examples 1-3 that the present invention further regulates the concentration of aluminum ions to be 0.01 mol / L to 0.05 mol / L, which can take into account obvious grain refinement, purity, and impurity element content within a better range. The average particle size D50 is between 500 nm and 800 nm, the purity is ≥97.5%, the aluminum content of impurity elements is 0.092% or less, and the overall performance of the obtained ultrafine cuprous oxide is better and more suitable for applications in different scenarios.

[0093] It can be seen from Example 6 that if the concentration of aluminum ions is too high, it will cause a significant increase in the aluminum impurity content in cuprous oxide, thereby affecting the purity of cuprous oxide.

[0094] (2) It can be seen from Example 1 and Comparative Example 1 that if no aluminum salt is added as a nucleation inducer, the particle size of cuprous oxide cannot be significantly refined, and the average particle size of cuprous oxide is still large.

[0095] (3) It can be seen from Example 1 and Comparative Examples 2-3 that if the aluminum salt is replaced with other metal salts, iron salt and zinc salt, it will not have an obvious effect on the refinement of cuprous oxide grains, and may even have the opposite effect, resulting in a significant increase in particle size, and more metal impurities will be introduced, which will have a greater impact on the purity of the prepared cuprous oxide.

[0096] In summary, the present invention uses the liquid phase precipitation method in combination with an aluminum salt as a nucleation inducer, which can refine the particle size of cuprous oxide particles, and then obtain ultrafine cuprous oxide with high sphericity, high stability, uniform morphology, narrow particle size distribution and uniform size; and the liquid phase precipitation method adopted by the present invention does not require harsh reaction conditions, has simple equipment, convenient operation, easy control of conditions, is suitable for large-scale production, and the aluminum salt has a wide source and low price. Therefore, it can achieve the preparation of ultrafine cuprous oxide with better performance at a lower cost, meet the preparation requirements of the present invention, and has good economic benefits.

[0097] The applicant declares that the above is only the specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A preparation method of ultrafine cuprous oxide, characterized in that, The preparation method includes the following steps: (1) First mix the copper salt mixed solution and the precipitant solution to obtain a copper hydroxide suspension; Among them, the copper salt mixed solution includes a copper salt, an aluminum salt, and a solvent; (2) Second mix the copper hydroxide suspension obtained in step (1) and the reducing agent solution to obtain ultrafine cuprous oxide.

2. The preparation method according to claim 1, wherein In the copper salt mixed solution in step (1), the concentration of aluminum ions is 0.002 mol / L to 0.1 mol / L, preferably 0.01 mol / L to 0.05 mol / L; Preferably, in the copper salt mixed solution in step (1), the concentration of copper ions is 0.1 mol / L to 1.26 mol / L, preferably 0.5 mol / L to 1 mol / L.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the precipitant in the precipitant solution in step (1) to the copper ions is (2.5 to 4):1, preferably (3 to 3.5):1; Preferably, the concentration of the precipitant solution in step (1) is 9 mol / L to 12 mol / L.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The molar ratio of the reducing agent in the reducing agent solution in step (2) to the copper in the copper hydroxide suspension is (0.5 to 1.5):1, preferably (0.75 to 1):1; Preferably, the concentration of the reducing agent solution in step (2) is 500 g / L to 1000 g / L, preferably 700 g / L to 900 g / L.

5. The preparation method according to any one of claims 1-4, characterized in that, The temperature of the second mixing in step (2) is 40°C to 70°C, preferably 55°C to 65°C.

6. The preparation method according to any one of claims 1-5, characterized in that, The precipitant solution in step (1) includes a sodium hydroxide solution and / or a potassium hydroxide solution; Preferably, in the copper salt mixed solution in step (1), the compound types of the copper salt and the aluminum salt each independently include a sulfate and / or a chloride; Preferably, the reducing agent solution in step (2) includes a glucose solution.

7. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: (1) First mix the copper salt mixed solution and the precipitant solution at room temperature, stir evenly to obtain a copper hydroxide suspension; Among them, the copper salt mixed solution includes a copper salt, an aluminum salt, and a solvent; in the copper salt mixed solution, the concentration of aluminum ions is 0.002 mol / L to 0.1 mol / L, and the concentration of copper ions is 0.1 mol / L to 1.26 mol / L; the molar ratio of the precipitant in the precipitant solution to the copper ions is (2.5 to 4):1; the concentration of the precipitant solution is 9 mol / L to 12 mol / L; (2) Second mix the copper hydroxide suspension obtained in step (1) and the reducing agent solution at 40°C to 70°C, maintain the temperature and stirring conditions for the reaction, and perform solid-liquid separation, washing, and drying on the obtained reaction solid particles to obtain ultrafine cuprous oxide; Among them, the molar ratio of the reducing agent in the reducing agent solution to the copper element in the copper hydroxide suspension is (0.5 to 1.5):1; the concentration of the reducing agent solution is 500 g / L to 1000 g / L.

8. An ultrafine cuprous oxide, characterized in that, The ultrafine cuprous oxide is prepared by the preparation method according to any one of claims 1-7.

9. The ultrafine cuprous oxide according to claim 8, wherein, The average particle size D50 of the ultrafine cuprous oxide is 500 nm to 1200 nm.

10. Application of ultrafine cuprous oxide, characterized in that, The ultrafine cuprous oxide prepared by the preparation method according to any one of claims 1 to 7, or the ultrafine cuprous oxide according to claim 8 or 9, is applied to photoelectrocatalysis, solar cells, sensors or antibacterial materials.

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