Preparation method of cuprous chloride cubes with different sizes

Abstract

The invention discloses a method for preparing CuCl cubes with different sizes by adopting a low-temperature liquid phase synthesis method. According to the method, a copper chloride solution is used as a reaction medium, CuCl is used as an oxidizing agent, and the reaction temperature can be controlled to be 25 DEG C. Foamy copper is added into the solution, and the foamy copper serves as a carrier of CuCl and also serves as a reducing agent. A copper source in CuCl comes from two parts, namely a copper chloride solution and foamy copper. CuCl cubes with different sizes can be prepared in a controlled manner by regulating and controlling the reaction time and the reaction temperature. Then, the synthesized cuprous chloride cubes are immediately wiped away with filter paper, finally, the cuprous chloride cubes are dried for 6 h in a drying oven at the temperature of 40 DEG C, and finally the cuprous chloride cubes are stored in the drying oven. The product prepared by the preparation method is high in purity, good in dispersity and good in crystal form and can be synthesized at normal temperature, the generated CuCl is low in cost and good in reproducibility, and the photocurrent density reaches up to 1.27 mA cm <-2 >.

Description

Technical Field

[0001] The present invention belongs to the field of materials, and more specifically relates to a method for preparing CuCl cubes of different sizes. Background Art

[0002] CuCl cubes have a larger specific surface area, size effect, amplification effect, anisotropy, surface modification and functionalization advantages, and are widely used in different fields, such as catalysis, energy, biomedicine, sensing, photodetectors, etc. Cuprous chloride cubes can be used as: (1) Catalysts: CuCl cubes can be used as catalysts, especially in organic synthesis reactions, to promote the reaction, improve the reaction efficiency and product yield. (2) Optoelectronic materials: CuCl cubes may be used to manufacture optoelectronic materials for detecting optical signals or performing optical signal conversion. The applicability of the above uses depends on the specific properties of CuCl cubes, such as particle size, morphology, surface modification, etc. In optoelectronic materials such as solar cells and solar panels, CuCl cubes can be used to improve the light absorption efficiency of the device, thereby enhancing the photoelectric conversion efficiency. (3) Sensors: CuCl cubes can be used as sensitive materials for biosensors to detect various chemical substances or biomarkers. (4) Antibacterial materials: Some cubes, including CuCl cubes, have antibacterial properties and can be used to manufacture antibacterial materials or medical devices.

[0003] Currently, the problems existing in the preparation of CuCl cubes are as follows: First, the stability problem. Cu(I) is extremely unstable in an aqueous solution state and is prone to disproportionation reactions. It leads to difficulties in preparation. Therefore, it is necessary to find ways to create the conditions for disproportional reaction to occur. Second, the preparation conditions are not easy to control. Precise control of reaction conditions such as temperature, solution concentration, pH value, etc. is required during the preparation process to ensure the formation of stable CuCl cubes. Minor changes in these conditions may affect the morphology and purity of the final product. Third, the product purity is low and the cubic morphology is difficult to control. During the preparation process, how to ensure that the generated CuCl has high purity and an ideal cubic morphology is a challenge. It is necessary to optimize the reaction conditions, select appropriate reactants and solvents, etc. to obtain high-quality CuCl cubes. Fourth, the operation is complex. The current synthesis methods involve multiple steps and complex operation processes, such as multiple washing, filtration, and drying steps, which increase the difficulty and cost of preparation. At the same time, some raw materials used in the preparation process (such as concentrated sulfuric acid, concentrated hydrochloric acid, etc.) are corrosive or toxic, posing high requirements for the safety of operators and environmental protection. Appropriate protective measures and wastewater treatment measures need to be taken to ensure the safety and environmental protection of the preparation process. In addition, when scaling up the laboratory-scale preparation method to industrial production, challenges may be faced in aspects such as raw material supply, equipment investment, and production cost. It is necessary to further optimize the preparation process, improve production efficiency, and reduce production costs. Summary of the Invention

[0004] The object of the present invention is to synthesize CuCl cubes with different particle sizes. The present invention is achieved through the following technical solutions:

[0005] A method for preparing cuprous chloride cubes of different sizes, the specific steps are as follows:

[0006] S1: Dissolve a certain amount of copper chloride (CuCl 2 ) in 20 mL of deionized water by ultrasonic treatment. After ultrasonic treatment, solution A is obtained. Place the glass bottle containing solution A in a constant temperature water bath.

[0007] S2: Ultrasonically wash a 1 cm * 1 cm copper foam with hydrochloric acid, ethanol, acetone, and water for 5 minutes each to obtain a clean copper foam B with no oxidation on the surface.

[0008] S3: Immediately immerse the washed copper foam B into solution A in the glass bottle and react for a certain period of time. After the reaction, wash the copper foam loaded with the product with deionized water, then immediately blot the water with filter paper, and then dry it in an oven at 40 °C for 6 hours, and recycle to obtain the product.

[0009] S4: Store the obtained product in a drying oven.

[0010] Further, in S1, the mass of copper chloride is 538 mg, and the concentration of solution A is 0.2 mol dm -3 .

[0011] Further, the Cu in S1 2+ is an oxidizing agent.

[0012] Further, the temperature of the constant temperature water bath is 25 °C.

[0013] Further, the copper foam in S2 is a reducing agent.

[0014] Further, the reaction time in S3 is 3 - 30 min.

[0015] A cuprous chloride cube with a size less than or equal to 200 nm is prepared by the above method.

[0016] Compared with the prior art, the present application has the following effects:

[0017] 1. In the present application, stable and pure-phase cubic CuCl is synthesized by a room temperature (25 °C) liquid-phase synthesis method. The size of the cube is affected by controlling the reaction time. When the reaction time is 3 - 5 min, the size of the CuCl cube is less than 200 nm, while a longer reaction time of 10 - 30 min will result in a relatively larger cube with a size of 200 nm. This method has a certain flexibility and controllability for preparing cuprous chloride with different average particle sizes, regular shapes, and good dispersibility, and is suitable for various application requirements. The oxidizing agent used is copper chloride, and the reducing agent is elemental copper from the copper foam. The solvent is deionized water, and no additional surfactant is required. The liquid-phase synthesis conditions can be achieved at room temperature, with a simple procedure and low cost, having practical applicability.

[0018] 2. Utilizing the property that CuCl is insoluble in water can promote the disproportional reaction, thereby improving the stability of the reaction; in the present application, different sizes can be obtained by controlling the reaction time at room temperature (25 °C), making the preparation conditions easy to control; the clean copper foam is fully reacted with the copper chloride solution, and then the obtained cuprous chloride is loaded on the copper foam substrate. After that, the CuCl loaded on the copper foam is washed clean with water and then immediately blotted dry with filter paper to avoid oxidation of CuCl by air, thereby obtaining high-purity cuprous chloride cubes; and by controlling different reaction times, cuprous chloride cubes with different sizes can be obtained; in the present application, copper chloride is dissolved in deionized water, and then a reaction solution is obtained through a constant temperature reaction. After that, the copper foam is ultrasonically washed and placed in the reaction solution, and then the copper foam loaded with the product is washed with deionized water, blotted with filter paper, and dried to obtain cuprous chloride cubes. The operation is simple and controllable, and there are no corrosive or toxic substances in the preparation process, which will not affect the safety of the operator and the environment, improving the safety and environmental protection of the preparation process.

[0019] 3. Using 0.1 mol dm -3 of CuCl 2The synthesized CuCl has a small amount and shows uneven granular shape, while the CuCl synthesized at a concentration of 0.3 mol dm -3 contains doped part of Cu 2 in the CuCl synthesized at a concentration of 0.3 mol dm 2 O. Therefore, the concentration of the selected CuCl solution is 0.2 mol dm -3 , and the weighed mass is 538 mg. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 FIG. is a scanning electron microscope (SEM) image of CuCl cubes with an average particle size of about 130 nm prepared according to the present invention.

[0021] Figure 2 FIG. is a scanning electron microscope (SEM) image of CuCl cubes with an average particle size of about 160 nm prepared according to the present invention.

[0022] Figure 3 FIG. is a scanning electron microscope (SEM) image of CuCl cubes with an average particle size of about 200 nm prepared according to the present invention.

[0023] Figure 4 FIG. is a scanning electron microscope (SEM) image of CuCl cubes with an average particle size of about 200 nm prepared according to the present invention.

[0024] Figure 5 FIG. is a scanning electron microscope (SEM) image of CuCl cubes with an average particle size of about 200 nm prepared according to the present invention.

[0025] Figure 6 FIG. is an X-ray diffraction photograph (XRD) of cuprous chloride cubes prepared in Examples 1-5. Figure 7 FIG. is an SEM image of a sample synthesized at a concentration of 0.3 mol dm‒3 CuCl2. Figure 8 FIG. is an XRD pattern of a sample synthesized at a concentration of 0.3 mol dm‒3 CuCl2.

[0026] Figure 9 FIG. is a transient photocurrent performance test graph (TPC) of cuprous chloride cube electrodes prepared in Examples 1-5.

[0027] Figure 10 FIG. is an alternating current impedance (EIS) spectrum of cuprous chloride cube electrodes prepared in Examples 1-5.

[0028] Figure 11 FIG. is a stability test of the CuCl-30 cube electrode prepared in Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0029] The reagents, methods, and equipment used in the present invention are all conventional reagents, methods, and equipment in the technical field. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available. The present invention will be further described in detail below with reference to the accompanying drawings.

[0030] Example 1

[0031] A method for preparing cuprous chloride cubes of different sizes is as follows:

[0032] S1: Dissolve 538 mg of copper chloride (CuCl 2 ) in 20 mL of deionized water by ultrasonic treatment. After ultrasonic treatment, solution A is obtained. Solution A is placed in a glass bottle in a water bath, and the glass bottle is kept at a constant temperature of 25 °C in a constant temperature water bath.

[0033] S2: Ultrasonically wash 1 cm × 1 cm copper foam with hydrochloric acid, ethanol, acetone, and water for 5 min each to obtain copper foam B with a clean surface without oxidation.

[0034] S3: Immediately immerse the washed copper foam B into solution A in the glass bottle, and let them react for 3 min. After the reaction, wash the copper foam loaded with the product with deionized water, then immediately blot dry with filter paper, and then dry in an oven at 40 °C for 6 h, and recover to obtain the product.

[0035] S4: Store the obtained product in a drying oven.

[0036] Example 2

[0037] A method for preparing cuprous chloride cubes of different sizes is as follows:

[0038] S1: Dissolve 538 mg of copper chloride (CuCl 2 ) in 20 mL of deionized water by ultrasonic treatment. After ultrasonic treatment, solution A is obtained. Solution A is placed in a glass bottle in a water bath, and the glass bottle is kept at a constant temperature of 25 °C in a constant temperature water bath.

[0039] S2: Ultrasonically wash 1 cm × 1 cm copper foam with hydrochloric acid, ethanol, acetone, and water for 5 min each to obtain copper foam B with a clean surface without oxidation.

[0040] S3: Immediately immerse the washed copper foam B into solution A in the glass bottle, and let them react for 5 min. After the reaction, wash the copper foam loaded with the product with deionized water, then immediately blot dry with filter paper, and then dry in an oven at 40 °C for 6 h, and recover to obtain the product.

[0041] S4: Store the obtained product in a drying oven.

[0042] Example 3

[0043] Method for preparing cuprous chloride cubes of different sizes, the specific steps are as follows:

[0044] S1: Ultrasonically dissolve 538 mg of copper chloride (CuCl 2 ) in 20 mL of deionized water. After ultrasonic treatment, solution A is obtained. Solution A is placed in a glass bottle in a water bath, and the glass bottle is kept at 25 °C in a constant temperature water bath.

[0045] S2: Ultrasonically wash 1 cm * 1 cm copper foam with hydrochloric acid, ethanol, acetone, and water for 5 minutes each to obtain clean copper foam B with no oxidation on the surface.

[0046] S3: Immediately immerse the washed copper foam B into solution A in the glass bottle, and let them react for 10 minutes. After the reaction, wash the copper foam loaded with the product with deionized water, then immediately blot dry with filter paper, and then dry in an oven at 40 °C for 6 hours, and recover to obtain the product.

[0047] S4: Store the obtained product in a drying oven.

[0048] Example 4

[0049] Method for preparing cuprous chloride cubes of different sizes, the specific steps are as follows:

[0050] S1: Ultrasonically dissolve 538 mg of copper chloride (CuCl 2 ) in 20 mL of deionized water. After ultrasonic treatment, solution A is obtained. Solution A is placed in a glass bottle in a water bath, and the glass bottle is kept at 25 °C in a constant temperature water bath.

[0051] S2: Ultrasonically wash 1 cm * 1 cm copper foam with hydrochloric acid, ethanol, acetone, and water for 5 minutes each to obtain clean copper foam B with no oxidation on the surface.

[0052] S3: Immediately immerse the washed copper foam B into solution A in the glass bottle, and let them react for 15 minutes. After the reaction, wash the copper foam loaded with the product with deionized water, then immediately blot dry with filter paper, and then dry in an oven at 40 °C for 6 hours, and recover to obtain the product.

[0053] S4: Store the obtained product in a drying oven.

[0054] Example 5

[0055] Method for preparing cuprous chloride cubes of different sizes, the specific steps are as follows:

[0056] S1: Ultrasonically dissolve 538 mg of copper chloride (CuCl 2 ) in 20 mL of deionized water. After ultrasonic treatment, solution A is obtained. Solution A is placed in a glass bottle in a water bath, and the glass bottle is kept at 25 °C in a constant temperature water bath.

[0057] S2: The 1 cm × 1 cm copper foam was ultrasonically washed with hydrochloric acid, ethanol, acetone, and water for 5 min each to obtain copper foam B with a non-oxidized and clean surface.

[0058] S3: The washed copper foam B was immediately immersed in solution A in a glass bottle, and the two reacted for 30 min. After the reaction, the copper foam loaded with the product was washed with deionized water, then immediately dried by blotting with filter paper, and then dried in an oven at 40 °C for 6 h, and recovered to obtain the product.

[0059] S4: The obtained product was stored in a drying oven.

[0060] Taking the products prepared in Examples 1–5 as the research objects, the present invention used scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques to characterize the phase structure of the materials, as described below:

[0061] (1) Morphology characterization

[0062] The structure of the prepared cube was detected using an S-4800 type SEM instrument, and the results are as Figure 1 shown in Fig. Figure 1 –5. As can be seen from Fig.

[0063] –5, the morphology of the material is a cube extrusion structure, and the size of the cube is 100–200 nm.

[0064] The structure of the prepared material was characterized using a Bruker D8 Advance type XRD, and the results are as Figure 6 shown in the figure. It can be seen from the figure that the crystal form of the prepared cube structure is a cubic crystal form, which is consistent with the standard card of CuCl, indicating that the CuCl material was successfully prepared. The three peaks marked with * belong to the peaks of copper foam.

[0065] (3) Transient photocurrent test

[0066] Using the CuCl loaded on the prepared copper foam as the photoanode, the saturated calomel electrode as the reference electrode, and the platinum sheet as the counter electrode, the photoelectrochemical hydrogen evolution performance of the CuCl cube was tested in a three-electrode system, and the electrolyte was 0.5 mol dm -3 Na 2 SO 4 . In the three-electrode system, the transient photocurrent test was used to evaluate the electrode material, and the results are as Figure 7 shown in the figure. The performance test shows that single CuCl has photoelectricity, and the transient photocurrent signal is as high as 1.27 mA cm -2 . The photocurrent test shows that the photocurrent signal is the largest at 30 min, that is, the carrier separation efficiency is the largest.

[0067] (4) AC impedance test

[0068] The ion transport and charge transfer impedance of the prepared active electrode material CuCl / CF were evaluated by electrochemical impedance spectroscopy. The CuCl-30 sample had a lower charge transfer impedance.

[0069] (5) Stability test

[0070] Taking CuCl-30 prepared in Example 5 as the research object, the CuCl cubes loaded on copper foam were directly used as the negative electrode material for photoelectrocatalytic hydrogen evolution, and a platinum sheet was used as the counter electrode to assemble a two-electrode system. The electrolyte was 0.5 mol dm – 3 Na 2 SO 4 , with an applied voltage of -0.655 V (0 V vs. RHE), and the photoelectrochemical stability with a constant current lasted for 2.5 h.

Claims

1. A method for preparing cuprous chloride cubes of different sizes, characterized in that: The specific steps are as follows: S1: ultrasonically dissolve a certain amount of copper chloride (CuCl2) in 20 mL of deionized water to obtain solution A, and place a glass bottle containing solution A in a constant temperature water area; S2: 1 cm*1 cm copper foam was ultrasonically washed with hydrochloric acid, ethanol, acetone, and water for 5 min each to obtain a clean copper foam B with no oxidation on the surface; S3: The cleaned copper foam B is immediately immersed in the solution A in the glass bottle and reacted for a certain period of time; after the reaction, the copper foam loaded with the product is washed with deionized water, and then the water is immediately absorbed with filter paper, and then dried in an oven at 40° C. for 6 hours, and recovered to obtain the product; S4: Store the obtained product in a drying oven.

2. A cuprous chloride cube having a size of less than or equal to 200 nm, characterized in that: The method according to claim 1 is used to prepare the product.

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