Preparation method of CuOHF nanoparticles

Abstract

The invention discloses a preparation method of CuOHF nanoparticles, and belongs to the technical field of nano material preparation. The CuOHF nano-particles are subjected to room-temperature co-precipitation and low-temperature annealing treatment, copper chloride dihydrate serves as a copper source, ammonium fluoride serves as a fluorine source, 75 vol% ethyl alcohol and deionized water serve as a room-temperature co-precipitation solution and a self-made cleaning solution, and after low-temperature sintering is conducted for 1-2 h at the temperature of 180 DEG C, the CuOHF nano-particle material can be obtained. The CuOHF nanoparticles have the characteristics of high purity and different particle sizes. The preparation method provided by the invention has the characteristics of easily available raw materials, mild reaction conditions, short period, safe and simple operation and the like, and has a good application prospect.

Description

Technical Field

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

[0002] With the extensive and in-depth research on nanomaterials, it is found that nanomaterials not only have the characteristics of large specific surface area, but also have the characteristics that as the particle size of nanomaterials decreases, the number of atoms on the surface of nanomaterials, surface energy and surface tension increase, which makes nanomaterials show small size effect, quantum size effect and tunnel effect, which in turn causes nanomaterials to show different properties from traditional materials in magnetic and optical properties. Especially low-micro nanomaterials, such as nanoparticle materials, have broad application prospects in catalysis and photodegradation.

[0003] There are many types 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 show better performance than their bulk materials in terms of 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, but there are few reports on the preparation of CuOHF. The few existing literature reports that one is produced by the hydrolysis of expensive and toxic CuF2·2H2O in an alkaline environment (Journal of the American Chemical Society, 1954, 76 (1): 263-264.), and the synthesized CuOHF often contains impurities, so it is relatively difficult to safely synthesize high-purity CuOHF by this method. Another approach is to use a high-pressure reactor and a hydrothermal method (CN 108455653A) to prepare a CuOHF material in the form of nanosheets, and the use of hexamethylenetetramine, which is easily explosive, is not conducive to large-scale industrial preparation. Therefore, the development of a method for preparing CuOHF with readily available raw materials and easy to scale, especially when it is in a nanoparticle state, is of great significance to the research and application of CuOHF. Summary of the invention

[0004] The 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 basis for the research and application of nano CuOHF materials in the fields of semiconductors and the like.

[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 amount of ethanol and deionized water, stir for 5 minutes, then add ammonium fluoride powder, continue stirring for 15 minutes, and then transfer all to 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, stir for 15 minutes, then drip the ammonium fluoride solution in the syringe into the copper chloride solution at a certain injection speed, stirring at a certain speed while dripping. After the dripping is completed, continue to stir at room temperature at this speed for 1 hour, then use a cleaning solution for centrifugal cleaning, and transfer the bottom precipitate in the centrifuge tube to the 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 the 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 the step b), the ethanol is 75 vol% ethanol, and the added amounts of 75 vol% ethanol and cupric chloride dihydrate are 20 ml and 1.27 g respectively; the injection speed is 43 ml / h, and the stirring speed while dropping 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, and 4 portions of the cleaning solution are used for centrifugal cleaning at a speed of 8900 rpm for 10 min for a total of 4 times, wherein 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 the temperature is 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 Bruker Advance D8 (Cu Kα radiation, The structure of the prepared material was determined by 2θ = 10-75°. The surface morphology of the prepared material was observed using a Hitachi S-4800 scanning electron microscope.

[0014] Depend on Figure 1 It can be seen that when the addition amount of copper chloride dihydrate and ammonium fluoride powder is 1.27g and 2.2g respectively, under the condition of annealing temperature of 180℃, when the annealing time is 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 when the annealing temperature is 180℃ and the annealing time is 1~2h, pure phase CuOHF material can be prepared. 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 in the form of nanoparticles, and the particle size varies, ranging from about 40 to 150nm. Figure 3 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 contains 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, which further proves that the product is CuOHF material. Figure 4 It can be seen that when the addition amounts of copper chloride dihydrate and ammonium fluoride powder are 1.27 g and 2.2 g respectively, after annealing at 180°C for 2 h, the obtained product contains 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 product obtained at different annealing times;

[0016] Figure 2 This is a scanning electron microscope image of the product obtained in Implementation Option 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 5min, then add 2.2g of ammonium fluoride powder, continue stirring for 15min, and then transfer all the solution to a 50ml syringe for use. In a 100ml beaker, add 20ml of 75vol% ethanol and 1.27g of copper chloride dihydrate powder, stir for 15min, then drop the ammonium fluoride solution in the syringe into the copper chloride solution at an injection speed of 43ml / h, stirring at 860 rpm while dropping, and continue stirring at 860 rpm at room temperature for 1h after the addition is complete. 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; the precipitate after stirring at room temperature for 1 hour was transferred to a 50 ml centrifuge tube, and after adding the cleaning solution, the precipitate was centrifuged at 8900 rpm for 10 minutes for a total of 4 times, and then the precipitate at the bottom of the centrifuge tube was transferred to a ceramic ark, and then directly transferred to a quartz tube furnace, and nitrogen was continuously introduced at a ventilation rate of 27 sccm, and the temperature was increased from 30°C to 180°C at a heating rate of 3°C / min. After heat preservation for 1 hour, it was cooled to room temperature with the furnace, and CuOHF nanoparticles were obtained. (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 5min, then add 2.2g of ammonium fluoride powder, continue stirring for 15min, and then transfer all the solution to a 50ml syringe for use. In a 100ml beaker, add 20ml of 75vol% ethanol and 1.27g of copper chloride dihydrate powder, stir for 15min, then drop the ammonium fluoride solution in the syringe into the copper chloride solution at an injection speed of 43ml / h, stirring at 860 rpm while dropping, and continue stirring at 860 rpm at room temperature for 1h after the addition is complete. 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; the precipitate after stirring at room temperature for 1 hour was transferred to a 50 ml centrifuge tube, and after adding the cleaning solution, the precipitate was centrifuged at 8900 rpm for 10 minutes for a total of 4 times, and then the precipitate at the bottom of the centrifuge tube was transferred to a ceramic ark, and then directly transferred to a quartz tube furnace, and nitrogen was continuously introduced at a ventilation rate of 27 sccm, and the temperature was increased from 30°C to 180°C at a heating rate of 3°C / min. After heat preservation for 2 hours, it was cooled to room temperature with the furnace, and CuOHF nanoparticles were obtained. (See Figure 1 Medium b and Figure 4 ).

Claims

1. A method for preparing CuOHF nanoparticles, comprising the following steps: a) In a 50 ml beaker, add appropriate amount of ethanol and deionized water, stir for 5 minutes, then add ammonium fluoride powder, continue stirring for 15 minutes, and then transfer all to a 50 ml syringe for later use; b) In a 100 ml beaker, add an appropriate amount of ethanol and copper chloride dihydrate powder, stir for 15 minutes, then drip the ammonium fluoride solution in the syringe into the copper chloride solution at a certain injection speed, stirring at a certain speed while dripping. After the dripping is completed, continue to stir at room temperature at this speed for 1 hour, then use a cleaning solution for centrifugal cleaning, and transfer the bottom precipitate in the centrifuge tube to the ceramic ark; 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. In the 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. In the step b), the ethanol is 75 vol% ethanol, and the added amounts of 75 vol% ethanol and cupric chloride dihydrate are 20 ml and 1.27 g, respectively.

2. The method for preparing CuOHF nanoparticles according to claim 1, characterized in that: In the step b), the injection speed is 43 ml / h, and the stirring speed while dropping and the stirring speed for 1 hour at room temperature are both 860 rpm.

3. The method for preparing CuOHF nanoparticles according to claim 1, characterized in that: In step b), the cleaning solution is composed 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 min for a total of four times, wherein the centrifuge tube is 50 ml in size.

4. The method for preparing CuOHF nanoparticles according to claim 1, characterized in that: 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 the temperature is kept at this temperature for 1 to 2 hours.

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