CN113800476B - Ultrasonic preparation method of nano metal oxide - Google Patents
Ultrasonic preparation method of nano metal oxide Download PDFInfo
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Abstract
The invention belongs to the technical field of nano metal oxide preparation, and relates to an ultrasonic preparation method of nano metal oxide. The ultrasonic preparation method of the nano metal oxide comprises the following steps: a step of treating a mixture including a metal simple substance and an acid solution using ultrasonic waves. The preparation process and equipment are simple in requirements, low in material cost, few in experimental parameters, mild in experimental conditions, capable of rapidly preparing the nanoscale metal oxide with the kilogram level or higher at normal temperature and normal pressure without additionally applying heat source and pressure, and suitable for industrial scale production.
Description
Technical Field
The invention belongs to the technical field of nano metal oxide preparation, and relates to an ultrasonic preparation method of nano metal oxide.
Background
Nano metal oxides have wide prospects in practical applications due to their unique physical and chemical properties, such as in high-efficiency catalysts, batteries, semiconductor devices, supercapacitors, energy storage, and magnetic and optical devices. In the scientific research of nano metal oxide materials, the synthesis of nano metal oxide is extremely important, and the difference of synthesis means has great influence on the microstructure and properties of the nano metal oxide.
The traditional synthesis method of the nano metal oxide comprises a hydrothermal method, a solvothermal method, a polyol method, a template method, a chemical vapor deposition method, an electrochemical synthesis method and the like. However, theseThe method generally needs to be completed in a high-temperature and/or high-pressure process, and takes a long time, as a preparation method of the gallium oxide nanorods disclosed in patent application CN108821331 a: heating gallium metal and a substrate to 1100-1200 ℃ in an inert atmosphere, introducing argon and oxygen, preserving heat for 1-2h, cooling, washing and drying to obtain gallium oxide nanorods; the preparation method of the ZnO nano porous sheet cluster is disclosed in Chinese patent CN104229866B, zinc nitrate and urea are taken as raw materials, dissolved by deionized water, added into a cylindrical bottomed container with the inner diameter of 10-50 mm, sealed, heated to 80-100 ℃ for normal pressure reaction for 8-12 hours, filtered, dried and roasted (250-500 ℃) to obtain the ZnO nano porous sheet cluster; as disclosed in chinese patent CN101318702B, a method for preparing nano-sheet of trioxide uses tungstic acid-based organic or inorganic layered hybrid micro/nano-belt (tube) as precursor, and removes organic matter between precursor layers by nitric acid oxidation to obtain tungstic acid (WO) 3 ·H 2 O) nanosheets, the reaction temperature is 15-50 ℃; the reaction time is 5-120h; tungstic acid (WO) 3 ·H 2 And O) heating the nano-sheet to 250-600 ℃ at a heating rate of 1-5 ℃/min, then preserving heat for 1-5h, and finally naturally cooling to room temperature to remove crystal water to obtain the tungsten trioxide nano-sheet. These preparation methods all need to be carried out at high temperature, and the prepared products have low yield, are not suitable for large-scale commercial production, and have great limitations.
Disclosure of Invention
The invention provides a method for preparing nano metal oxide with the kilogram grade or above by ultrasonic treatment without additional application of heat source and pressure at normal temperature and normal pressure.
The above object of the invention is achieved by the following technical scheme:
an ultrasonic preparation method of nano metal oxide, comprising the following steps: a step of treating a mixture including a metal simple substance and an acid solution using ultrasonic waves.
Preferably, the ultrasonic preparation method is carried out at a temperature of 45 ℃ or less and a pressure of 150KPa or less.
Preferably, the ultrasonic preparation method is carried out at a temperature of 40 ℃ or less and a pressure of 102KPa or less.
Preferably, the ultrasonic preparation method is carried out at a temperature of 37 ℃ or less and a pressure of 102KPa or less.
Preferably, the ultrasonic preparation method is carried out at a temperature of less than or equal to 30 ℃ and a pressure of less than or equal to 102 KPa.
Preferably, the acid solution is one of hydrochloric acid solution, acetic acid solution, phosphoric acid solution, sulfuric acid solution, nitric acid solution, and aqua regia. Aqua regia is concentrated hydrochloric acid and concentrated nitric acid in a volume ratio of 3:1, and a mixed strong acid formed by the method.
Preferably, the concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution and the nitric acid solution is more than or equal to 0.1mol/L.
Preferably, the concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution and the nitric acid solution is more than or equal to 0.3mol/L.
Preferably, the concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution and the nitric acid solution is more than or equal to 0.5mol/L.
Preferably, the metal simple substance is one or more of iron, chromium, cobalt, cadmium, nickel, tin, zinc and tungsten.
Preferably, the purity of the metal simple substance is more than or equal to 90 percent.
Preferably, the purity of the metal simple substance is more than or equal to 95 percent.
Preferably, the purity of the metal simple substance is more than or equal to 99 percent.
Preferably, the metal element is in a block or powder form.
Preferably, when the metal element is in a powder form, the metal element has an average particle diameter of 5 to 5000nm.
Preferably, when the metal element is in the form of powder, the metal element has an average particle diameter of 10 to 500nm.
Preferably, the ratio of the mass (g) of the metal element to the volume (ml) of the acid solution is (0.001-0.3): 1g/ml.
Preferably, the mixture comprising the elemental metal and the acid solution is placed in an ultrasonic instrument for ultrasonic treatment.
Preferably, the ultrasonic instrument is one or more of an ultrasonic cell disruption instrument, an ultrasonic cleaner and an ultrasonic material stripper.
Preferably, the ultrasonic treatment frequency is 20-100KHz, and the power is more than or equal to 100W.
Preferably, the ultrasonic treatment frequency is 20-50KHz, and the power is more than or equal to 200W.
Preferably, the method prepares nano metal oxides of milligram grade or more.
Preferably, the method prepares nano metal oxides above kilogram level.
Preferably, the nano metal oxide is prepared as a zero-dimensional, one-dimensional or two-dimensional nano material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention prepares nano metal oxide by using ultrasonic treatment of the mixture comprising metal simple substance and acid solution, and can rapidly prepare nano metal oxide at normal temperature and pressure without additionally applying heat source and pressure;
(2) The experimental raw materials for preparing the nano metal oxide are very simple, only simple metal substances and acid solutions are needed, the experimental equipment is simple in requirements, the preparation of the nano metal oxide can be realized by adopting an ultrasonic instrument, and the preparation cost is low;
(3) The preparation process of the nano metal oxide is simple, the experimental parameters are few, the experimental conditions are mild, and the purity and the yield of the product are high;
(4) The invention can realize the rapid preparation of nano metal oxide with the kilogram level or more, and is suitable for industrialized mass production;
(5) The invention can realize the morphology regulation of the nano metal oxide by changing the process conditions.
Drawings
FIG. 1 (a) is an X-ray diffraction pattern (XRD) of the ZnO nano-sheet obtained in example 2, and FIG. 1 (b) is a Raman spectrum (Raman) of the ZnO nano-sheet obtained in example 2 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the ZnO nano-sheets obtained in example 2 of the present invention;
FIG. 3 is a High Resolution Transmission Electron Microscope (HRTEM) image of the ZnO nanosheets of example 2 of the present invention;
FIG. 4 is a scanning image of XPS full spectrum energy of 0 to 1200eV of the ZnO nano-sheet obtained in example 2 of the present invention;
FIG. 5 (a) is WO obtained in example 4 3 ·H 2 X-ray diffraction pattern (XRD) of O nanoplatelets, FIG. 5 (b) is WO obtained in example 4 of the present invention 3 ·H 2 Raman spectrum of O (Raman);
FIG. 6 is WO of example 4 of the present invention 3 ·H 2 Scanning Electron Microscope (SEM) images of O nanoplatelets;
FIG. 7 shows WO obtained in example 4 of the present invention 3 ·H 2 High Resolution Transmission Electron Microscope (HRTEM) images of O nanoplatelets;
FIG. 8 shows WO obtained in example 4 of the present invention 3 ·H 2 XPS full spectrum energy scan of 0 to 1200eV for O nanoplatelets.
Detailed Description
The method for preparing the nano metal oxide according to the present invention will be described in detail below, and the technical or scientific terms used at this time have meanings commonly understood by those skilled in the art of the present invention unless otherwise defined.
An ultrasonic preparation method of nano metal oxide, comprising the following steps: a step of treating a mixture including a metal simple substance and an acid solution using ultrasonic waves.
The nano metal oxide prepared by the invention refers to a metal oxide with at least one dimension in a three-dimensional space in a nano size (nano size refers to a length size less than or equal to 100 nm), and can be a zero-dimensional, one-dimensional or two-dimensional nano material. Zero-dimensional nanomaterials refer to three dimensions that are all in the nanometer size range, such as nanoparticles, etc.; one-dimensional nanomaterial refers to a material having two dimensions in the nanometer size range, such as nanowires, nanorods, nanotubes, etc.; two-dimensional nanomaterials refer to a dimension in the nanometer size range, such as nanoplatelets, nanofilms, and the like.
Ultrasonic treatment, namely placing a mixture comprising a metal simple substance and an acid solution into an ultrasonic instrument for ultrasonic treatment; preferably, the mixture of the metal simple substance and the acid solution is placed in a reaction bottle, and then the reaction bottle is placed in an ultrasonic instrument for ultrasonic treatment, wherein the reaction bottle can be a glass container.
Any ultrasonic apparatus that can release ultrasonic waves and can hold a reaction flask containing a mixture of elemental metal and an acid solution can be used in the present invention, preferably one or more of an ultrasonic cytoclasis apparatus, an ultrasonic cleaner, and an ultrasonic material stripper.
Applying ultrasonic waves to the mixture comprising the metal simple substance and the acid solution, wherein the frequency of the applied ultrasonic waves is preferably 20-100KHz, and the power of the ultrasonic waves is preferably more than or equal to 100W; when the nano metal oxide is prepared in a large amount, the ultrasonic treatment frequency is preferably 20-50KHz, and the ultrasonic power is preferably more than or equal to 200W. The ultrasonic treatment time is different according to the ultrasonic power and the metal simple substance: when the same ultrasonic instrument is used, the higher the applied ultrasonic power is, the faster the nano metal oxide preparation speed is, and the shorter the ultrasonic treatment time is; the ultrasonic treatment time is different for different metal simple substances. The ultrasonic treatment time is preferably 1 to 20 hours, more preferably 1 to 10 hours, still more preferably 1 to 6 hours by adjusting the ultrasonic power for different metal elements.
The metal simple substance is the metal simple substance corresponding to the nano metal oxide to be prepared, and the purity of the metal simple substance is more than or equal to 90 percent, preferably more than or equal to 95 percent, and further preferably more than or equal to 99 percent. The higher the purity of the metal simple substance is, the higher the purity of the nano metal oxide can be obtained. The metal simple substance is preferably one or more of iron, chromium, cobalt, cadmium, nickel, tin, zinc and tungsten, and the nano metal oxides correspondingly obtained by the metal simple substances are respectively iron oxide, chromium oxide, cobalt oxide, cadmium oxide, nickel oxide, tin oxide, zinc oxide and tungsten oxide.
The metal simple substance is in a block shape or a powder shape, and when the metal simple substance is in a powder shape, the average particle size of the metal simple substance is preferably 5-5000nm; further preferably, the average particle diameter is 10 to 500nm. The average particle diameter is defined as an average of the particle diameters of 100 particles arbitrarily selected among the observed particles when the particles are observed by using an electron microscope such as a transmission electron microscope or a scanning electron microscope. The smaller the average particle size of the metal simple substance powder, the faster the reaction speed, and the shorter the time for preparing the nano metal oxide.
The addition amount of the metal element is not particularly limited, and it is preferable that the mass of the metal element to the volume ratio of the acid solution is (0.001 to 0.3): 1 in g/ml. The smaller the addition amount of the metal simple substance is relative to the volume of the acid solution, the faster the reaction speed is.
The acid solution of the present invention is preferably one of hydrochloric acid solution, acetic acid solution, phosphoric acid solution, sulfuric acid solution, nitric acid solution, and aqua regia. Preferably, the molar concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution and the nitric acid solution is more than or equal to 0.1mol/L; further preferably, the molar concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution and the nitric acid solution is more than or equal to 0.3mol/L; in the further step, the molar concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution and the nitric acid solution is preferably more than or equal to 0.5mol/L. The upper limit of the molar concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution and the nitric acid solution is the maximum molar concentration of the concentrated hydrochloric acid, the concentrated acetic acid, the concentrated phosphoric acid, the concentrated sulfuric acid and the concentrated nitric acid respectively.
The ultrasonic preparation method of the nano metal oxide can be carried out at the temperature of less than or equal to 45 ℃ and the pressure of less than or equal to 150KPa, can be carried out at the temperature of less than or equal to 37 ℃ and the pressure of less than or equal to 150KPa, can be carried out at the temperature of less than or equal to 30 ℃ and the pressure of less than or equal to 120KPa, can be carried out at the temperature of less than or equal to 37 ℃ and the pressure of less than or equal to 120KPa, can be carried out at the temperature of less than or equal to 30 ℃ and the pressure of less than or equal to 102 KPa. Preferably, the ultrasonic preparation method is carried out at normal temperature and normal pressure, wherein the normal temperature is 5-40 ℃, and the normal pressure is 1 standard atmospheric pressure.
The ultrasonic preparation method of the nano metal oxide does not need additional heat source and pressure, namely an ultrasonic instrument does not need heating and pressurizing, and the ultrasonic treatment is carried out on the mixture comprising the metal simple substance and the acid solution at normal temperature and pressure. The ultrasonic preparation method can realize the mass preparation of the nano metal oxide at normal temperature and normal pressure.
The ultrasonic preparation method of the nano metal oxide can prepare nano metal oxide with milligram grade or more. The weight of the prepared nano metal oxide depends on the treatment volume of an ultrasonic instrument, the treatment volume of the ultrasonic instrument is large, and the more the treated mixture comprising the metal simple substance and the acid solution is, the more the mass of the prepared nano metal oxide is.
The invention can prepare nano metal oxide with the kilogram grade or more by adopting a high-capacity ultrasonic instrument, thereby realizing industrial scale production.
Hereinafter, the technical scheme of the present invention will be further described and illustrated by specific examples. However, these embodiments are exemplary, and the present disclosure is not limited thereto. Unless otherwise indicated, all materials used in the following examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
In the following examples and comparative examples, the average particle diameter of nano Zn powder (purity: 99.8%) was 150nm, the average particle diameter of nano tungsten powder (purity: 99.8%) was 500nm, the ambient temperature was 25℃and the ambient pressure was 101.33KPa.
Example 1
15mL of 0.5mol/L dilute nitric acid solution is measured and put into a glass small bottle, 1mmol (65.38 mg) of nano Zn powder is added into the glass small bottle, the glass small bottle is placed into an ultrasonic two-dimensional material stripper (scientific-CHF-5A, new Chinese sesame) for ultrasonic treatment, the ultrasonic treatment frequency is 40KHz, and the power is adjusted to 360W; ultrasonic treatment is carried out for 2 hours under the stirring condition; naturally cooling to room temperature after ultrasonic treatment, carrying out suction filtration, preserving and recycling the obtained solution, reducing reagent consumption, washing the obtained white powder with 75v/v% ethanol solution for 3 times, and finally drying at 80 ℃ for 12 hours to obtain the ZnO nano-sheet material. The mass of the obtained ZnO nano-sheet is 75.3mg after weighing.
Example 2
Measuring 30L of 0.8mol/L HCl solution in a large-mouth glass bottle, adding 20mmol (1307.6 g) of nano Zn powder into the large-mouth glass bottle, placing the large-mouth glass bottle in an ultrasonic two-dimensional material stripper (scientific-CHF-5A, new Chinese sesame) for ultrasonic treatment, wherein the ultrasonic treatment frequency is 40KHz, and the power is adjusted to 720W; ultrasonic treatment is carried out for 3.5 hours under the stirring condition; naturally cooling to room temperature after ultrasonic treatment, carrying out suction filtration, preserving and recycling the obtained solution, reducing reagent consumption, washing the obtained white powder with 80v/v% ethanol solution for 3 times, and finally drying at 75 ℃ for 12 hours to obtain the ZnO nano-sheet material. The mass of the ZnO nano-sheet obtained by weighing is 1494g.
FIG. 1 (a) is an X-ray diffraction pattern (XRD) of the ZnO nano-sheet obtained in example 2. XRD patterns show that the ZnO nano-sheets obtained by the method are wurtzite type, the space group is P63mc (JCPLDS 36-1451), and no impurity peak is detected, which indicates that the method obtains the ZnO nano-sheets with high purity. Meanwhile, fig. 1 (b) is a Raman spectrum (Raman) of the ZnO nanoplatelets obtained in example 2 of the present invention, the excitation wavelength of the laser is 532nm, and no impurity peak is detected in the Raman spectrum, which indicates that the pure ZnO nanoplatelets are obtained in the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the ZnO nano-sheets obtained in example 2 of the present invention; from the figure, it can be seen that the preparation method of the invention obtains ZnO in the form of large nano-sheets.
FIG. 3 is a High Resolution Transmission Electron Microscope (HRTEM) image of the ZnO nanosheets obtained in example 2 of the present invention. Wherein (a) shows that ZnO is in a sheet structure, corresponding to the SEM image of fig. 2; (b) The distance between adjacent crystal faces was measured to be 0.28nm, which was shown to have a good match with the d-spacing value of the (100) crystal face in the lead zinc ore ZnO.
In order to determine the chemical composition of the elements in the ZnO nanoplatelets, X-ray photoelectron spectroscopy (XPS) test was performed, and fig. 4 is an XPS full spectrum energy scan of 0 to 1200eV of the ZnO nanoplatelets obtained in example 2 of the present invention, in which only Zn, O elements and trace carbon are present, indicating that the ZnO nanoplatelets of high purity were prepared.
The principle of the present invention for preparing ZnO nanoplatelets will be explained as follows: nano Zn powder quilt H + Oxidation to Zn 2+ Next, zn 2+ OH with water - Reaction to Zn (OH) 2 ，Zn(OH) 2 Hydrolysis gradually forms ZnO seed crystals during high intensity ultrasound due to instability. At the same time, znO is a polar oxide(the polar surface is divided into a Zn surface and an O surface), and the first principle calculation shows that the adsorption energy of the O surface and H is lower than that of Zn, so that the O surface is covered by H to inhibit the adsorption of Zn and prevent the vertical growth of zinc oxide. At this time OH - And Zn 2+ Can only be adsorbed on a nonpolar surface, promotes the radial growth of ZnO and finally forms ZnO nano-sheets.
The traditional ZnO nano material has very bad synthesis conditions, such as high temperature and high pressure, long reaction time, poor separation effect of reaction products and the like. The method can rapidly prepare a large amount of ZnO nano-sheets at normal temperature and pressure by ultrasonic treatment under the acid solution without additional application of heat source and pressure.
Example 3
9mL of concentrated HCl and 3mL of concentrated HNO are measured 3 Forming a mixed solvent in a glass vial, adding 1mmol (183.84 mg) of metal nano W powder into the mixed solvent, placing the glass vial in an ultrasonic two-dimensional material stripper (scientific-CHF-5A, new Chinese sesame) for ultrasonic treatment, wherein the ultrasonic treatment frequency is 40KHz, and the power is adjusted to 360W; ultrasonic treatment is carried out for 2 hours under the stirring condition; naturally cooling to room temperature after ultrasonic treatment, filtering, preserving and recycling the obtained solution, reducing reagent consumption, washing the obtained yellow powder with 75v/v% ethanol solution for 3 times, and drying at 80deg.C for 12 hr to obtain WO 3 ·H 2 O nanoplatelet structures. WO obtained by weighing 3 ·H 2 The mass of the O nano-sheet is 149.91mg, and the yield is 60%.
Example 4
36L of concentrated HCl and 12L of concentrated HNO are measured 3 Forming a mixed solvent in a large-mouth glass bottle, adding 10mol (1838.4 g) of metal nano W powder into the mixed solvent, placing the large-mouth glass bottle in an ultrasonic two-dimensional material stripper (scientific-CHF-5A, new Chinese sesame) for ultrasonic treatment, wherein the ultrasonic treatment frequency is 40KHz, and the power is adjusted to 720W; ultrasonic treatment is carried out for 3 hours under the stirring condition; naturally cooling to room temperature after ultrasonic treatment, filtering, preserving and recycling the obtained solution, reducing reagent consumption, washing the obtained yellow powder with 75v/v% ethanol solution for 3 times, and drying at 85deg.C for 12 hr to obtain WO 3 ·H 2 O nanoplatelet structures. WO obtained by weighing 3 The mass of the nano-sheet is 1510.26g.
FIG. 5 (a) is WO obtained in example 4 3 ·H 2 X-ray diffraction pattern (XRD) of O nanoplatelets. No impurity peak was detected by XRD pattern, indicating that the invention obtains high purity WO 3 A nano-sheet. FIG. 5 (b) is the WO of example 4 of the present invention 3 The Raman spectrum of the product is 532nm, and no impurity peak is detected in the Raman spectrum, which shows that the invention obtains pure WO 3 A nano-sheet.
FIG. 6 shows WO obtained in example 4 of the present invention 3 ·H 2 Scanning Electron Microscope (SEM) images of O nanoplatelets; as can be seen from the figure, the preparation method of the invention obtains the WO in the form of large nano-sheets 3 。WO 3 The nanoplatelets tend to be more stable in order to reduce the overall formation energy, self-assembling to form a spherical structure.
FIG. 7 shows WO obtained in example 4 of the present invention 3 ·H 2 High Resolution Transmission Electron Microscope (HRTEM) image of O nanoplatelets. Wherein 7 (a) shows WO 3 Is a sheet structure, and corresponds to the SEM image of FIG. 6; (b) The distance between adjacent crystal faces was measured to be 0.37nm, as compared with WO 3 The d-spacing values of the intermediate (120) crystal planes have a good match.
To determine WO 3 Chemical composition of elements in the nanoplatelets, X-ray photoelectron Spectrometry (XPS) was performed, FIG. 8 shows WO obtained in example 4 of the present invention 3 XPS full spectrum energy scan of 0 to 1200eV of nano sheet, wherein only W, O element and trace carbon exist, indicating that high purity WO is prepared 3 A nano-sheet.
WO 3 The synthesis conditions of the nano material are very bad, such as high temperature, high pressure, long reaction time, poor separation effect of reaction products and the like. The invention can rapidly prepare a large amount of high-purity WO at normal temperature and pressure by ultrasonic treatment without additional application of heat source and pressure 3 A nano-sheet.
The preparation of WO according to the present invention will be explained below 3 ·H 2 Principle of O nanoplatelets: first, tungsten powder is oxidized to WO by reaction with aqua regia solution 4 2- After that, WO is applied under low pH conditions 4 2- Will form WO 3 ·H 2 And (3) inoculating the seed crystal. By ultrasonic treatment of the resulting WO 3 ·H 2 O nano-particles are used as a seed layer for growth and grow up continuously, and dissolved WO 4 2- Providing a tungsten source and finally, realizing WO 3 ·H 2 Growth of O nanoplatelets.
The ultrasonic preparation method of the nano metal oxide can prepare and obtain the product with the weight of more than kilogram at normal temperature and normal pressure, realizes simple, rapid and mass preparation of the nano metal oxide, and is easy to realize industrial mass production.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (12)
1. An ultrasonic preparation method of nano metal oxide is characterized in that the nano metal oxide is WO 3 The ultrasonic preparation method of the nano sheet comprises the following steps: placing the mixture comprising the metal simple substance and the acid solution into an ultrasonic instrument for ultrasonic treatment;
the metal simple substance is tungsten;
the acid solution is aqua regia;
the volume ratio of the metal simple substance to the acid solution is (0.001-0.3): 1 g/ml;
the ultrasonic treatment frequency is 20-100KHz, and the power is more than or equal to 100W.
2. The ultrasonic preparation method of the nano metal oxide according to claim 1, wherein the ultrasonic preparation method is carried out at the temperature of less than or equal to 45 ℃ and the pressure of less than or equal to 150 KPa.
3. The ultrasonic preparation method of the nano metal oxide according to claim 1, wherein the ultrasonic preparation method is carried out at a temperature of 40 ℃ or less and a pressure of 102KPa or less.
4. The ultrasonic preparation method of the nano metal oxide according to claim 1, wherein the purity of the metal simple substance is more than or equal to 90%.
5. The ultrasonic preparation method of the nano metal oxide according to claim 1, wherein the purity of the metal simple substance is more than or equal to 95%.
6. The ultrasonic preparation method of nano metal oxide according to claim 1, wherein the metal simple substance is in a block shape or a powder shape.
7. The ultrasonic preparation method of nano metal oxide according to claim 6, wherein when the metal simple substance is in a powder form, the average particle size of the metal simple substance is 5-5000nm.
8. The ultrasonic preparation method of nano metal oxide according to claim 6, wherein when the metal simple substance is in a powder form, the average particle size of the metal simple substance is 10-500nm.
9. The method for preparing nano metal oxide according to claim 1, wherein the ultrasonic instrument is one or more of an ultrasonic cell disruption instrument, an ultrasonic cleaner, and an ultrasonic material stripper.
10. The ultrasonic preparation method of the nano metal oxide according to claim 1, wherein the ultrasonic treatment frequency is 20-50KHz, and the power is more than or equal to 200W.
11. The ultrasonic preparation method of nano metal oxide according to claim 1, wherein the method is used for preparing nano metal oxide with milligram grade or more.
12. The ultrasonic preparation method of nano metal oxide according to claim 1, wherein the method is used for preparing nano metal oxide with a kilogram level or more.
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