A Cu2(OH)3X-B heterojunction composite material, preparation method and application thereof

Abstract

The invention belongs to the field of nanomaterial technology, and discloses a method for preparing a nano-flaky 2D / 2D Cu2(OH)3X-B heterojunction composite material. First, 1mmol of 200-mesh magnesium boride powder is dispersed in 20-200mL of deionized water solvent; 1mmol of copper nitrate is fully dissolved in 20-200mL of deionized water, and then the above solution is poured into it, and 0.5-5mL of hydrochloric acid solution is added to accelerate the reaction process; 1mol of halogen source is added to form a halogen-substituted hydroxy copper halide, and after ultrasonication for 10mins, it is stirred for 3 days, filtered and centrifuged, and freeze-dried to obtain a gray-brown product. The 2D / 2D Cu2(OH)3X-B prepared by the present invention has a nano-flaky structure, and is uniform in size and has good dispersibility. It can be applied to the fields of optics, magnetism, catalysis, etc.

Description

Technical Field

[0001] The present invention belongs to the technical field of nanomaterials, and in particular relates to a 2D / 2D Cu2(OH)3X-B heterojunction composite material, a preparation method and applications thereof. Background Art

[0002] Two-dimensional (2D) materials, such as graphene, transition metal hydroxides, hexagonal boron nitride, Mxenes and boron, have a wide range of applications in various fields such as magnetism, optics, sensing, and catalysis due to their large surface area, adjustable electronic structure, and high mechanical properties. Polyhydroxy copper halide (Cu2(OH)3X) has a layered morphology with a polycrystalline structure. At the same time, the presence of hydroxyl bonds in the lattice improves the catalytic activity of the material by enhancing the electrochemical reaction, and is widely used in catalyzing the Fenton reaction. The halide ions in its structure have high electronegativity and can significantly change the surface polarity and dielectric constant of the material. Patents CN201910287714.8 and CN202110385503.5 only provide a method for preparing pure hydroxy copper halide nanomaterials, and do not provide a strategy for constructing Cu2(OH)3X heterojunctions. Although individual 2D polyhydroxy copper halides possess certain application advantages, different material preparation methods can produce Cu2(OH)3X nanomaterials with significant variations in crystal quality, size, morphology, and thickness, limiting their application and widespread adoption. Boron (B), the lightest metalloid, readily forms highly dispersed BB bonds due to its electron-deficient nature, endowing it with unique electronic, optical, thermal, and chemical properties, making it suitable for the fabrication of lightweight nanodevices. The formation of 2D / 2D heterojunctions with rectifying contact interfaces, formed by combining Cu2(OH)3X-B nanosheets, offers unique catalytic advantages, such as abundant catalytically active sites, favorable charge transfer, and enhanced light absorption. However, the development of 2D / 2D composite materials presents significant challenges. Therefore, developing methods for preparing Cu2(OH)3X-B composites is of great practical significance.

[0003] Through the above analysis, the problems and defects of the existing technology are: there is currently no preparation method for 2D / 2D Cu2(OH)3X-B heterojunction composite materials, which limits the application and promotion of 2D / 2D heterojunction composite materials. Summary of the Invention

[0004] In response to the problems existing in the prior art, the present invention provides a 2D / 2D Cu2(OH)3X-B heterojunction composite material, a preparation method and applications thereof.

[0005] The present invention adopts the following technical solutions:

[0006] A method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material comprises the following steps:

[0007] Step 1: dispersing magnesium boride powder in deionized water solvent and stirring;

[0008] Step 2: Dissolve the soluble copper salt in deionized water, add the above solution, add hydrochloric acid solution, and stir further;

[0009] Step 3: adding a halogen source, ultrasonicating, stirring, filtering, centrifuging, and freeze-drying to obtain a nanosheet-like 2D / 2D Cu2(OH)3X-B heterojunction composite material.

[0010] Furthermore, in step 1, 1 mmol of magnesium boride powder was dispersed in 20-200 mL of deionized water solvent and stirred for 10 minutes.

[0011] Furthermore, the particles of the magnesium boride powder are 200 meshes.

[0012] Furthermore, in step 2, 1 mmol of soluble copper salt is fully dissolved in 20-200 mL of deionized water, and then the above solution is poured into the mixture, and 0.5-5 mL of hydrochloric acid solution is added to accelerate the reaction process.

[0013] Furthermore, the soluble copper salt is copper nitrate.

[0014] Furthermore, the concentration of the hydrochloric acid is 36%.

[0015] Furthermore, in step 3, 1 mmol of halogen source was added, and after ultrasonication for 10 mins, the mixture was stirred, filtered, centrifuged, and freeze-dried to obtain a nanosheet-like 2D / 2D Cu2(OH)3X-B heterojunction composite material.

[0016] Furthermore, the halogen source includes one or more of sodium chloride, sodium bromide, sodium fluoride, potassium chloride, potassium chloride, potassium bromide, potassium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium fluoride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium fluoride.

[0017] Furthermore, the stirring time is 3 days.

[0018] The present invention also provides an application of the heterojunction composite material, which is applied in the fields of optics, magnetism, and catalysis.

[0019] Compared with the prior art, the present invention has the following technical advantages:

[0020] (1) The technical solution to be protected by the present invention has a simple process and does not require high temperature and high pressure; the reagents used in the solution of the present invention are low in cost, and the solvent used is deionized water; and the prepared 2D / 2D Cu2(OH)3X-B heterojunction composite material has high purity, high crystallinity, good dispersibility, and has certain commercial value.

[0021] (2) There is no report on 2D / 2D Cu2(OH)3X-B heterojunction composite materials at present, which fills the gap in new Cu2(OH)3X-B heterojunction synthesis technology at home and abroad. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a scanning electron microscope (SEM) image of the product obtained in Example 1 of the present invention;

[0023] Figure 2 is the X-ray diffraction (XRD) pattern of the product obtained in Example 1 of the present invention;

[0024] Figure 3 is a scanning electron microscope (SEM) image of the product obtained without adding a halogen source;

[0025] Figure 4 is the X-ray diffraction (XRD) pattern of the product obtained without adding a halogen source. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0027] 1. Explanatory Examples In order to enable those skilled in the art to fully understand how to implement the present invention, this section provides an illustrative example that expands upon the technical solutions of the claims.

[0028] The method for preparing the 2D / 2D Cu2(OH)3X-B heterojunction composite material provided in an embodiment of the present invention comprises the following steps:

[0029] S101, dispersing magnesium boride powder in deionized water solvent;

[0030] S102, fully dissolving copper nitrate in deionized water, then pouring the above solution into it, and adding hydrochloric acid solution to accelerate the reaction process;

[0031] S103, adding a halogen source, ultrasonicating, stirring, filtering, centrifuging, and freeze-drying to obtain a 2D / 2DCu2(OH)3X-B heterojunction composite material.

[0032] The magnesium boride powder in step S101 in the embodiment of the present invention should have a particle size of less than 200 meshes to facilitate dispersion of the material and subsequent reactions.

[0033] The hydrochloric acid in step S102 in the embodiment of the present invention is 36% concentrated hydrochloric acid, which mainly serves to accelerate the reaction process.

[0034] The halogen source in step S103 in the embodiment of the present invention is generally a metal halogen salt: sodium chloride, sodium bromide, sodium fluoride, potassium chloride, potassium chloride, potassium bromide, potassium fluoride; or an organic ammonium salt containing halogen ions: tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium fluoride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium fluoride, etc.

[0035] In order to make the present invention more fully disclosed, it is described below through more specific embodiments.

[0036] Example 1

[0037] A method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material comprises the following steps:

[0038] (1) Disperse 1 mmol of 200-mesh magnesium boride powder in 30 mL of deionized water and stir for 10 min.

[0039] (2) Dissolve 1 mmol of copper nitrate in 30 mL of deionized water, add the above solution, and add 1 mL of hydrochloric acid solution;

[0040] (3) 1 mmol of tetraethylammonium bromide was added, and after ultrasonication for 10 mins, the mixture was stirred for 3 days, filtered and centrifuged, and freeze-dried to obtain a 2D / 2D Cu2(OH)3X-B heterojunction composite material.

[0041] Example 2

[0042] A method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material comprises the following steps:

[0043] (1) Disperse 1 mmol of 200-mesh magnesium boride powder in 35 mL of deionized water and stir for 10 min.

[0044] (2) Dissolve 1 mmol of copper nitrate in 35 mL of deionized water, add the above solution, and add 1 mL of hydrochloric acid solution;

[0045] (3) 1 mmol of sodium chloride was added, and the mixture was ultrasonicated for 10 mins, stirred for 3 days, filtered, centrifuged, and freeze-dried to obtain a 2D / 2D Cu2(OH)3X-B heterojunction composite material.

[0046] Example 3

[0047] A method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material comprises the following steps:

[0048] (1) Disperse 1 mmol of 200-mesh magnesium boride powder in 34 mL of deionized water and stir for 10 min.

[0049] (2) Dissolve 1 mmol of copper nitrate in 32 mL of deionized water, add the above solution, and add 1 mL of hydrochloric acid solution;

[0050] (3) 1 mmol of tetraethylammonium chloride was added, and after ultrasonication for 10 mins, the mixture was stirred for 3 days, filtered and centrifuged, and freeze-dried to obtain a 2D / 2D Cu2(OH)3X-B heterojunction composite material.

[0051] Example 4

[0052] A method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material comprises the following steps:

[0053] (1) Disperse 1 mmol of 200-mesh magnesium boride powder in 30 mL of deionized water and stir for 10 min.

[0054] (2) Dissolve 1 mmol of copper nitrate in 45 mL of deionized water, add the above solution, and add 1.8 mL of hydrochloric acid solution;

[0055] (3) 1 mmol potassium bromide was added, ultrasonicated for 10 mins, stirred for 3 days, filtered and centrifuged, and freeze-dried to obtain a 2D / 2D Cu2(OH)3X-B heterojunction composite material.

[0056] Example 5

[0057] A method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material comprises the following steps:

[0058] (1) Disperse 1 mmol of 200-mesh magnesium boride powder in 40 mL of deionized water and stir for 10 min.

[0059] (2) Dissolve 1 mmol of copper nitrate in 40 mL of deionized water, add the above solution, and add 1.5 mL of hydrochloric acid solution;

[0060] (3) 1 mmol of hexadecyltrimethylammonium chloride was added, ultrasonicated for 10 mins, stirred for 3 days, filtered and centrifuged, and freeze-dried to obtain a 2D / 2D Cu2(OH)3X-B heterojunction composite material.

[0061] Example 6

[0062] A method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material comprises the following steps:

[0063] (1) Disperse 1 mmol of 200-mesh magnesium boride powder in 30 mL of deionized water and stir for 10 min.

[0064] (2) Dissolve 1 mmol of copper nitrate in 30 mL of deionized water, add the above solution, and add 1 mL of hydrochloric acid solution;

[0065] (3) 1 mmol of hexadecyltrimethylammonium fluoride was added, ultrasonicated for 10 mins, stirred for 3 days, filtered and centrifuged, and freeze-dried to obtain a 2D / 2D Cu2(OH)3X-B heterojunction composite material.

[0066] 2. Application Examples: In order to demonstrate the creativity and technical value of the technical solution of the present invention, this section provides application examples of the claimed technical solution on specific products or related technologies.

[0067] The materials produced by the method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material provided in the embodiments of the present invention can be widely used in fields such as optics, magnetism, and catalysis. Currently, no similar methods for preparing such composite materials exist, both domestically and internationally, demonstrating the inventiveness and technical value of the present invention's technical solution.

[0068] 3. Evidence of the effects of the embodiments: The embodiments of the present invention have achieved some positive effects during the development or use process, and indeed have great advantages over the existing technology. The following content describes them with reference to the data, charts, etc. of the experimental process.

[0069] The 2D / 2D Cu2(OH)3X-B heterojunction prepared in Example 1 is stripped of magnesium boride by electrochemical etching, as shown in FIG. Figure 1 As shown in the figure, it can be seen that the morphology of the material is a uniform nanosheet structure with uniform size and high crystallinity; Figure 2 As shown in Figure 2, XRD shows that the material has a high degree of crystallinity, which perfectly matches the PDF#45-1309 card (Cu2(OH)3Br), indicating that the magnesium boride has reacted completely and has been successfully exfoliated into nanosheets. Figure 3-4 As shown in the figure, it can be seen that the material morphology is also a nanosheet structure. XRD shows that the material has a high degree of crystallinity, which perfectly matches the PDF#45-0594 card (Cu2(OH)3(NO3)), and a hydroxy copper nitrate / B nanocomposite material can be obtained.

[0070] The above description is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by any technician familiar with this technical field within the technical scope disclosed by the present invention and within the spirit and principles of the present invention should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing a 2D / 2D Cu2(OH)3X-B heterojunction composite material, characterized in that: The following steps are involved: Step 1: dispersing magnesium boride powder in deionized water solvent and stirring; Step 2: Dissolve the soluble copper salt in deionized water, add the above solution, add hydrochloric acid solution, and stir further; Step 3: adding a halogen source, sonicating, stirring, filtering, centrifuging, and freeze-drying to obtain a nanosheet-like 2D / 2D Cu2(OH)3X-B heterojunction composite material; In step 1, 1 mmol of magnesium boride powder was dispersed in 20-200 mL of deionized water and stirred for 10 min. The particles of the magnesium boride powder are 200 mesh; In step 2, 1 mmol of soluble copper salt is fully dissolved in 20-200 mL of deionized water, and then the above solution is poured into the mixture, and 0.5-5 mL of hydrochloric acid solution is added to accelerate the reaction process.

2. The method for preparing a heterojunction composite material according to claim 1, wherein: The soluble copper salt is copper nitrate.

3. The method for preparing a heterojunction composite material according to claim 1, wherein: The concentration of the hydrochloric acid is 36%.

4. The method for preparing a heterojunction composite material according to claim 1, wherein: In step 3, 1 mmol of halogen source was added, ultrasonicated for 10 min, stirred for 3 days, filtered and centrifuged, and freeze-dried to obtain a nanosheet-like 2D / 2D Cu2(OH)3X-B heterojunction composite material.

5. The method for preparing the heterojunction composite material according to claim 4, wherein: The halogen source includes one or more of sodium chloride, sodium bromide, sodium fluoride, potassium chloride, potassium chloride, potassium bromide, potassium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium fluoride, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium fluoride.

6. A heterojunction composite material prepared according to the method according to any one of claims 1 to 5.

7. An application of the heterojunction composite material according to claim 6, characterized in that: Applications include optics, magnetism, and catalysis.

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