A method for preparing CuOHF nanoparticles

Abstract

"A method for preparing CuOHF nanoparticles" belongs to the technical field of nanomaterial preparation. The CuOHF nanoparticles are prepared using room temperature coprecipitation and low temperature annealing, using cupric chloride dihydrate as the copper source, ammonium fluoride as the fluorine source, 75 vol% ethanol and deionized water as the room temperature coprecipitation solution, and a homemade cleaning solution. After low-temperature sintering at 180°C for 1-2 hours, the CuOHF nanoparticles are obtained. These CuOHF nanoparticles are characterized by high purity and a variety of particle sizes. This preparation method, characterized by readily available raw materials, mild reaction conditions, a short cycle time, and safe and simple operation, has promising application prospects.

Description

Technical Field

[0001] The invention discloses a method for preparing CuOHF nanoparticles, belonging to the technical field of nanomaterial preparation. Technical Background

[0002] Extensive and in-depth research on nanomaterials has revealed that nanomaterials not only possess a large specific surface area, but also exhibit characteristics such as an increase in the number of surface atoms, surface energy, and surface tension as the particle size decreases. This leads to the small size effect, quantum size effect, and tunneling effect, which in turn leads to nanomaterials exhibiting properties that differ from those of traditional materials in magnetic and optical properties. Low-micron nanomaterials, such as nanoparticles, have broad application prospects in catalysis and photodegradation.

[0003] There are many types of metal cations of MOHF, and common metal cations include Cu, Co, Ni, Mg, Zn, Cd, etc. Most MOHF nanomaterials, such as nanoparticles, nanorods (nanowires), and nanosheets, often exhibit superior performance to their bulk counterparts in photodegradation, electrocatalysis, and quantum dot-sensitized batteries. Among them, CuOHF is a wide-bandgap semiconductor material with potential applications in short-wavelength light-emitting devices, ultraviolet light detection, and high-temperature, high-power electronic devices. However, there are few reports on the preparation of CuOHF. The few existing literature reports that CuOHF is produced by the hydrolysis of expensive and somewhat toxic CuF2·2H2O in an alkaline environment (Journal of the American Chemical Society, 1954, 76(1): 263-264.). The synthesized CuOHF often contains impurities, so it is relatively difficult to safely synthesize high-purity CuOHF using this method. Another approach is to use a hydrothermal method in a high-pressure reactor (CN 108455653A). The CuOHF material is prepared in the form of nanosheets and uses hexamethylenetetramine, which is easily explosive. This is not conducive to practical large-scale industrial production. Therefore, developing a method for preparing CuOHF with readily available raw materials and ease of scale, especially in the form of nanoparticles, is of great significance to the research and application of CuOHF. Summary of the Invention

[0004] The present invention provides a method with readily available raw materials, mild reaction conditions, short cycle, and safe and simple operation. The method utilizes room temperature coprecipitation and low temperature annealing treatment to prepare CuOHF nanoparticles with high purity, which is particularly suitable for batch preparation and provides a foundation for the research and application of nano-CuOHF materials in fields such as semiconductors.

[0005] The present invention provides a method for preparing CuOHF nanoparticles, which comprises the following steps:

[0006] a) In a 50 ml beaker, add appropriate amounts of ethanol and deionized water, stir for 5 minutes, then add ammonium fluoride powder and continue stirring for 15 minutes. Transfer the entire amount into a 50 ml syringe for later use.

[0007] b) In a 100 ml beaker, add an appropriate amount of ethanol and copper chloride dihydrate powder. After stirring for 15 minutes, add the ammonium fluoride solution in the syringe dropwise to the copper chloride solution at a certain injection rate while stirring at a certain speed. After the addition is complete, continue stirring at the same speed at room temperature for 1 hour. Then, use a cleaning solution to centrifuge and transfer the bottom precipitate in the centrifuge tube to a ceramic ark.

[0008] c) placing the ceramic ark containing the precipitate in a quartz tube furnace, continuously introducing nitrogen, and heating from 30°C to a predetermined temperature at a heating rate of 3°C / min. After a period of heat preservation, the ark is cooled to room temperature along with the furnace to obtain CuOHF nanoparticles.

[0009] In step a), the ethanol is 75 vol% ethanol, and the added amounts of 75 vol% ethanol, deionized water and ammonium fluoride are 20 ml, 3 ml and 2.2 g, respectively.

[0010] In step b), the ethanol is 75 vol% ethanol, and the amounts of 75 vol% ethanol and copper chloride dihydrate added are 20 ml and 1.27 g, respectively. The injection rate is 43 ml / h, and the stirring speed during dropwise addition and the stirring speed for 1 hour at room temperature are both 860 rpm. The cleaning solution consists of 10 ml of 75 vol% ethanol and 30 ml of deionized water. Four portions of the cleaning solution are centrifuged at 8900 rpm for 10 minutes for a total of four cleaning cycles. The centrifuge tube is 50 ml in size.

[0011] The precipitate obtained by centrifugation in step c) is directly transferred to a quartz tube furnace for treatment without drying; at the same time, the temperature is raised to 180° C. at a heating rate of 3° C. / min under a nitrogen ventilation rate of 27 sccm and kept at this temperature for 1 to 2 hours.

[0012] Compared with other methods for preparing CuOHF, this method not only greatly simplifies the preparation process, but also has relatively low requirements for reaction conditions, is suitable for large-scale production, reduces production costs, and shortens the production cycle; more importantly, this method can stably prepare pure-phase CuOHF nanoparticles.

[0013] The X-ray powder diffractometer was used with a Bruker Advance D8 (Cu Kα radiation, The structure of the prepared materials was determined using a Hitachi S-4800 scanning electron microscope to observe the surface morphology of the prepared materials.

[0014] Depend on Figure 1 It can be seen that when the addition amounts of copper chloride dihydrate and ammonium fluoride powder are 1.27g and 2.2g respectively, under the condition of annealing temperature of 180℃ and annealing time of 1h (a) and 2h (b), the diffraction peaks of the obtained products are all attributed to the diffraction peaks of CuOHF (JCPDS card No.07-0306), and no obvious diffraction peaks of other substances are observed, indicating that pure phase CuOHF material can be prepared under the condition of annealing temperature of 180℃ and annealing time of 1~2h. Figure 2 It can be seen that when the addition amount of copper chloride dihydrate and ammonium fluoride powder is 1.27g and 2.2g respectively, after annealing at 180℃ for 1h, the obtained product is nano-particles with different particle sizes, ranging from about 40 to 150nm. Figure 3 It can be seen that when the amount of copper chloride dihydrate and ammonium fluoride powder added was 1.27g and 2.2g respectively, after annealing at 180℃ for 1h, the product contained Cu, F and O elements (H is a light element and cannot be detected by energy spectrum), and n (copper ion): n (fluoride ion) = 32.91% / 32.98%≈0.998, further proving that the product is CuOHF material. Figure 4 It can be seen that when the addition amounts of copper chloride dihydrate and ammonium fluoride powders were 1.27 g and 2.2 g, respectively, and after annealing at 180°C for 2 h, the obtained product contained Cu, F, and O elements (H is a light element and cannot be detected by energy spectrum), and n (copper ion): n (fluoride ion) = 32.38% / 33.29%≈0.973, further proving that the product is CuOHF material. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 is the X-ray diffraction pattern of the products obtained at different annealing times;

[0016] Figure 2 This is a scanning electron microscope image of the product obtained in embodiment 1:

[0017] Figure 3 is the energy spectrum of the product obtained in Implementation Option 1;

[0018] Figure 4 It is the energy spectrum diagram of the product obtained by implementation scheme 2. DETAILED DESCRIPTION

[0019] 1. In a 50ml beaker, add 20ml of 75vol% ethanol and 3ml of deionized water. Stir for 5 minutes, then add 2.2g of ammonium fluoride powder. Continue stirring for 15 minutes, then transfer the entire solution to a 50ml syringe for later use. In a 100ml beaker, add 20ml of 75vol% ethanol and 1.27g of copper chloride dihydrate powder. Stir for 15 minutes, then add the ammonium fluoride solution in the syringe dropwise to the copper chloride solution at a rate of 43ml / h, stirring at 860 rpm. After the addition is complete, continue stirring at 860 rpm at room temperature for 1 hour. At the same time, 4 portions of cleaning solution were prepared for use, each of which consisted of 10 ml of 75 vol% ethanol and 30 ml of deionized water. After stirring at room temperature for 1 hour, the precipitate was transferred to a 50 ml centrifuge tube. After adding the cleaning solution, the mixture was centrifuged at 8900 rpm for 10 minutes for a total of 4 centrifugal washes. The precipitate at the bottom of the centrifuge tube was then transferred to a ceramic ark, which was then directly transferred to a quartz tube furnace. Nitrogen was continuously introduced at a ventilation rate of 27 sccm. The temperature was increased from 30°C to 180°C at a heating rate of 3°C / min. After the temperature was maintained for 1 hour, the mixture was cooled to room temperature in the furnace to obtain CuOHF nanoparticles. (See Figure 1 Middle a, Figure 2 and Figure 3 ).

[0020] 2. In a 50ml beaker, add 20ml of 75vol% ethanol and 3ml of deionized water. Stir for 5 minutes, then add 2.2g of ammonium fluoride powder. Continue stirring for 15 minutes, then transfer the entire solution to a 50ml syringe for later use. In a 100ml beaker, add 20ml of 75vol% ethanol and 1.27g of copper chloride dihydrate powder. Stir for 15 minutes, then add the ammonium fluoride solution from the syringe dropwise to the copper chloride solution at a rate of 43ml / h, stirring at 860 rpm. After the addition is complete, continue stirring at 860 rpm at room temperature for 1 hour. At the same time, 4 portions of cleaning solution were prepared for use, each of which consisted of 10 ml of 75 vol% ethanol and 30 ml of deionized water. After stirring at room temperature for 1 hour, the precipitate was transferred to a 50 ml centrifuge tube. After adding the cleaning solution, the mixture was centrifuged at 8900 rpm for 10 minutes for a total of 4 centrifugal washes. The precipitate at the bottom of the centrifuge tube was then transferred to a ceramic ark, which was then directly transferred to a quartz tube furnace. Nitrogen was continuously introduced at a ventilation rate of 27 sccm. The temperature was increased from 30°C to 180°C at a heating rate of 3°C / min. After a 2-hour heat treatment, the mixture was cooled to room temperature in the furnace to obtain CuOHF nanoparticles. (See Figure 1 Zhongb and Figure 4 ).

Claims

1. A method for preparing CuOHF nanoparticles, comprising the following steps: a) In a 50 ml beaker, add appropriate amounts of ethanol and deionized water, stir for 5 minutes, then add ammonium fluoride powder and continue stirring for 15 minutes. Transfer the entire amount into a 50 ml syringe for later use. b) In a 100 ml beaker, add an appropriate amount of ethanol and copper chloride dihydrate powder. After stirring for 15 minutes, add the ammonium fluoride solution in the syringe dropwise to the copper chloride solution at a certain injection rate while stirring at a certain speed. After the addition is complete, continue stirring at the same speed at room temperature for 1 hour. Then, use a cleaning solution to centrifuge and transfer the bottom precipitate in the centrifuge tube to a ceramic ark. c) placing the ceramic ark containing the precipitate in a quartz tube furnace, continuously introducing nitrogen, heating the ark from 30°C to a predetermined temperature at a heating rate of 3°C / min, holding the ark for a period of time, and then cooling the ark to room temperature to obtain CuOHF nanoparticles; In step a), the ethanol is 75 vol% ethanol, and the amounts of 75 vol% ethanol, deionized water, and ammonium fluoride added are 20 ml, 3 ml, and 2.2 g, respectively; In step b), the ethanol is 75 vol% ethanol, and the added amounts of 75 vol% ethanol and copper chloride dihydrate are 20 ml and 1.27 g, respectively.

2. The method for preparing CuOHF nanoparticles according to claim 1, wherein: In step b), the injection rate is 43 ml / h, and the stirring rate during dropwise addition and the stirring rate for 1 hour at room temperature are both 860 rpm.

3. The method for preparing CuOHF nanoparticles according to claim 1, wherein: In step b), the cleaning solution consists of 10 ml of 75 vol% ethanol and 30 ml of deionized water. Four portions of the cleaning solution are used for centrifugation at 8900 rpm for 10 min, and the centrifuge tube is 50 ml in size.

4. The method for preparing CuOHF nanoparticles according to claim 1, wherein: The precipitate obtained by centrifugation in step c) is directly transferred to a quartz tube furnace for treatment without drying; at the same time, the temperature is raised to 180° C. at a heating rate of 3° C. / min under a nitrogen ventilation rate of 27 sccm and kept at this temperature for 1 to 2 hours.

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