CN113800476A - 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: and treating a mixture comprising the simple metal and the acid solution by using ultrasonic waves. The preparation process and equipment have the advantages of simple requirements, low material cost, few experimental parameters, mild experimental conditions, no additional heat source and pressure, capability of quickly preparing the nano metal oxide with the level of over kilogram at normal temperature and normal pressure, and suitability for industrial large-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
Due to their unique physical and chemical properties, nano-metal oxides have a wide prospect in practical applications, such as 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 oxides is extremely important, and the difference of synthetic means has great influence on the microstructure and properties of the nano metal oxides.
The traditional synthesis methods of the nano metal oxide include 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, these methods usually need to be completed in a high temperature and/or high pressure process and are time-consuming, such as the preparation method of gallium oxide nanorods disclosed in patent application CN 108821331A: heating metal gallium and a substrate to 1100-1200 ℃ in an inert atmosphere, introducing argon and oxygen, preserving the temperature for 1-2h, cooling, washing and drying to obtain a gallium oxide nanorod; according to the preparation method of the ZnO nano porous sheet cluster disclosed by the Chinese patent CN104229866B, zinc nitrate and urea are used as raw materials, the raw materials are dissolved by deionized water, added into a cylindrical container with a bottom and an inner diameter of 10-50 mm, sealed, heated to 80-100 ℃ and reacted for 8-12 hours under normal pressure, and filtered, dried and roasted (250-500 ℃) to obtain the ZnO nano porous sheet cluster; for another example, as disclosed in chinese patent CN101318702B, a method for preparing trioxide nano-sheets is disclosed, which uses tungstic acid-based organic or inorganic layered hybrid micro/nano-ribbons (tubes) as precursors, and removes organic matter between the precursor layers by nitric acid oxidation to obtain tungstic acid (WO)3·H2O) nano-sheets, the reaction temperature is 15-50 ℃; the reaction time is 5-120 h; the obtained tungstic acid (WO)3·H2O) heating the nanosheet to 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 nanosheet. These preparation methods are all carried out at high temperature, and the prepared products have low yield, are not suitable for large-scale commercial production and have great limitation.
Disclosure of Invention
Aiming at the defects of the existing synthesis method of the nano metal oxide, the invention provides a method for preparing the nano metal oxide with the level of over kilogram under normal temperature and normal pressure by ultrasonic treatment without additionally applying a heat source and pressure.
The above object of the present invention is achieved by the following technical solutions:
an ultrasonic preparation method of nano metal oxide comprises the following steps: and treating a mixture comprising the simple metal and the acid solution by using ultrasonic waves.
Preferably, 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.
Preferably, the ultrasonic preparation method is carried out at the temperature of less than or equal to 40 ℃ and the pressure of less than or equal to 102 KPa.
Preferably, the ultrasonic preparation method is carried out at the temperature of less than or equal to 37 ℃ and the pressure of less than or equal to 102 KPa.
Preferably, the ultrasonic preparation method is 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 acid solution is one of a hydrochloric acid solution, an acetic acid solution, a phosphoric acid solution, a sulfuric acid solution, a nitric acid solution and aqua regia. Aqua regia is concentrated hydrochloric acid and concentrated nitric acid, and the volume ratio of aqua regia to concentrated nitric acid is 3: 1, and 1, forming a mixed strong acid.
Preferably, the concentration of the hydrochloric acid solution, acetic acid solution, phosphoric acid solution, sulfuric acid solution or nitric acid solution is not less than 0.1 mol/L.
Preferably, the concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution or the nitric acid solution is not less than 0.3 mol/L.
Preferably, the concentration of the hydrochloric acid solution, the acetic acid solution, the phosphoric acid solution, the sulfuric acid solution or the nitric acid solution is not less than 0.5 mol/L.
Preferably, the elementary metal 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%.
Preferably, the purity of the metal simple substance is more than or equal to 95%.
Preferably, the purity of the metal simple substance is more than or equal to 99%.
Preferably, the metal simple substance is in a block shape or a powder shape.
Preferably, when the elementary metal is in a powder form, the average particle size of the elementary metal is 5-5000 nm.
Preferably, when the elementary metal is in a powder form, the average particle size of the elementary metal is 10-500 nm.
Preferably, the ratio of the mass (g) of the metal simple substance to the volume (ml) of the acid solution is (0.001-0.3): 1 g/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 disruptor, 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 is used for preparing the nano metal oxide with the milligram level or more.
Preferably, the method is used for preparing the nanometer metal oxide with the kilogram level or more.
Preferably, the prepared nano metal oxide is 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 uses ultrasonic treatment to prepare the nanometer metal oxide by the mixture of the metal simple substance and the acid solution, does not need to additionally apply heat source and pressure, and can quickly prepare the nanometer metal oxide at normal temperature and normal pressure;
(2) the experimental raw materials for preparing the nano metal oxide are very simple, only metal simple substances and an acid solution are needed, the requirement on experimental equipment is simple, the preparation of the nano 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 the nanometer metal oxide with the kilogram level and is suitable for the industrialized mass production;
(5) the invention can realize the shape 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 nanosheet obtained in example 2, and fig. 1(b) is a Raman spectrum (Raman) of the ZnO nanosheet obtained in example 2 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of ZnO nanosheets obtained in example 2 of the present invention;
FIG. 3 is a High Resolution Transmission Electron Microscopy (HRTEM) image of ZnO nanosheets of example 2 of the present invention;
FIG. 4 is an XPS survey of full spectrum energy scans at 0 to 1200eV of ZnO nanoplates obtained from example 2 of the present invention;
FIG. 5(a) shows WO obtained in example 43·H2X-ray diffraction pattern (XRD) of O nanosheet, and FIG. 5(b) is WO obtained in example 4 of the present invention3·H2Raman spectrogram (Raman) of O;
FIG. 6 shows WO of example 4 of the present invention3·H2Scanning Electron Microscope (SEM) images of O nanoplates;
FIG. 7 shows WO obtained in example 4 of the present invention3·H2High Resolution Transmission Electron Microscopy (HRTEM) images of O nanoplates;
FIG. 8 shows WO obtained in example 4 of the present invention3·H2XPS full spectrum energy scan of O nanoplate from 0 to 1200 eV.
Detailed Description
The method for preparing the nano metal oxide of the present invention will be described in detail below, and technical terms or scientific terms used at this time have meanings that are generally understood by those skilled in the art of the present invention, if not otherwise defined.
An ultrasonic preparation method of nano metal oxide comprises the following steps: and treating a mixture comprising the simple metal and the acid solution by 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 (the nano size refers to the 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 nanomaterials with three dimensions in the nanometer size range, such as nanoparticles; the one-dimensional nano material refers to two dimensions in a nano size range, such as a nanowire, a nanorod, a nanotube and the like; two-dimensional nanomaterials refer to materials with one dimension in the nanometer size range, such as nanosheets, nanofilms, and the like.
Ultrasonic treatment, namely placing a mixture comprising a metal simple substance and an acid solution in 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 instrument that can release ultrasonic waves and can accommodate a reaction flask containing a mixture of elemental metal and an acid solution can be used in the present invention, and is preferably one or more of an ultrasonic cell disruptor, an ultrasonic cleaner, and an ultrasonic material stripper.
Applying ultrasonic waves to a 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 scale, 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 preparation speed of the nano metal oxide 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, and still more preferably 1 to 6 hours by adjusting the ultrasonic power for different metal simple substances.
The metal simple substance is a 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%, preferably more than or equal to 95%, and more preferably more than or equal to 99%. The higher the purity of the metal simple substance is, the more highly pure 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 obtained by corresponding to 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 5-5000 nm; more preferably, the average particle diameter is 10 to 500 nm. The average particle diameter is defined as an average value of particle diameters of 100 particles arbitrarily selected among the observed particles by an observation method using an electron microscope such as a transmission electron microscope or a scanning electron microscope. The smaller the average particle size of the metal elementary powder is, the faster the reaction speed is, and the shorter the time for preparing the nano metal oxide is.
The addition amount of the simple metal is not particularly limited, and the mass to volume ratio of the simple metal to the acid solution is preferably (0.001-0.3): 1 in g/ml. The smaller the amount of the simple metal added relative to the volume of the acid solution, the faster the reaction speed.
The acid solution of the 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 0.1 mol/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 0.3 mol/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 0.5 mol/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 concentrated hydrochloric acid, concentrated acetic acid, concentrated phosphoric acid, concentrated sulfuric acid and 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 150KPa, 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 120KPa, can be carried out at the temperature of less than or equal to 37 ℃ and the pressure of less than or equal to 102KPa, and 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 refers to 5-40 ℃, and the normal pressure refers to 1 standard atmospheric pressure.
The ultrasonic preparation method of the nano metal oxide does not need to additionally apply heat source and pressure, namely an ultrasonic instrument does not need to heat and pressurize, and the mixture containing the metal simple substance and the acid solution is subjected to ultrasonic treatment at normal temperature and normal pressure. The ultrasonic preparation method of the invention can realize the mass preparation of the nano metal oxide under normal temperature and normal pressure.
The ultrasonic preparation method of the nano metal oxide can prepare the nano metal oxide with the milligram level or more. The weight of the prepared nano metal oxide depends on the processing volume of an ultrasonic instrument, the processing volume of the ultrasonic instrument is large, and the more mixture comprising the metal simple substance and the acid solution is processed, the more the nano metal oxide is prepared.
The invention can adopt a large-capacity ultrasonic instrument to prepare the nanometer metal oxide with the kilogram level or more, thereby realizing the industrial scale production.
Hereinafter, the technical solution 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 specified, the raw materials used in the following specific examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art.
In the following examples and comparative examples, the average particle size of nano Zn powder (purity 99.8%) was 150nm, the average particle size of nano tungsten powder (purity 99.8%) was 500nm, the ambient temperature was 25 ℃ and the ambient pressure was 101.33 KPa.
Example 1
Measuring 15mL of 0.5mol/L dilute nitric acid solution into a glass vial, adding 1mmol (65.38mg) of nano Zn powder, placing the glass vial into an ultrasonic two-dimensional material stripper (Scientz-CHF-5A, New Chinese Ganoderma) 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; and naturally cooling to room temperature after ultrasonic treatment, carrying out suction filtration, storing the obtained solution for recycling, reducing the consumption of a reagent, washing the obtained white powder for 3 times by using a 75 v/v% ethanol solution, and finally drying at 80 ℃ for 12h to obtain the ZnO nanosheet material. The obtained ZnO nanosheet is 75.3mg in mass by weighing.
Example 2
Measuring 30L of 0.8mol/L HCl solution in a wide-mouth glass bottle, adding 20mmol (1307.6g) of nano Zn powder, placing the wide-mouth glass bottle in an ultrasonic two-dimensional material stripper (Scientz-CHF-5A, Xinzhi, China) 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; and naturally cooling to room temperature after ultrasonic treatment, carrying out suction filtration, storing the obtained solution for recycling, reducing the consumption of a reagent, washing the obtained white powder for 3 times by using an 80 v/v% ethanol solution, and finally drying at 75 ℃ for 12h to obtain the ZnO nanosheet material. The obtained ZnO nanosheet is 1494g in mass by weighing.
Fig. 1(a) is an X-ray diffraction pattern (XRD) of the ZnO nanosheet obtained in example 2. An XRD (X-ray diffraction) spectrum shows that the ZnO nanosheet obtained by the method is wurtzite, the space group is P63mc (JCPDS 36-1451), and no impurity peak is detected, so that the high-purity ZnO nanosheet obtained by the method is shown. Meanwhile, fig. 1(b) is a Raman spectrogram (Raman) of the ZnO nanosheet obtained in example 2 of the present invention, the laser excitation wavelength of the test is 532nm, and no impurity peak is detected in the Raman spectrogram, which indicates that the pure ZnO nanosheet obtained in the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of ZnO nanosheets obtained in example 2 of the present invention; as can be seen from the figure, the preparation method of the invention obtains ZnO in the form of large-sheet nanosheets.
Fig. 3 is a high-resolution transmission electron microscope (HRTEM) image of ZnO nanosheets obtained in example 2 of the present invention. Wherein (a) shows that ZnO is a lamellar structure, in concert with the SEM picture of fig. 2; (b) the measured distance between adjacent crystal faces is 0.28nm, and the d-spacing value of the crystal face (100) in the lead-zinc ore ZnO is well matched.
In order to determine the chemical composition of elements in the ZnO nanosheet, an X-ray photoelectron spectroscopy (XPS) test is performed, fig. 4 is an XPS full spectrum energy scan of 0 to 1200eV of the ZnO nanosheet obtained in example 2 of the present invention, and only Zn, O elements and trace carbon exist in the map, indicating that the ZnO nanosheet with high purity is prepared.
The principle of the present invention for preparing ZnO nanosheets will be explained below: nano Zn powder quilt H+By oxidation to Zn2+Then, Zn2+With OH in water-Reaction to form Zn (OH)2，Zn(OH)2ZnO seed crystals are gradually formed by hydrolysis in the high-intensity ultrasonic process due to instability. Meanwhile, ZnO is a polar oxide (polar surfaces are divided into a Zn surface and an O surface), and calculation combined with a first principle 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 the vertical growth of zinc oxide is prevented. OH at this time-And Zn2+Can only be adsorbed on a nonpolar surface, promotes the radial growth of ZnO, and finally forms the ZnO nano-sheet.
The traditional ZnO nano material has very bad synthesis conditions, such as high temperature, high pressure, long reaction time, poor separation effect of reaction products and the like. According to the invention, a large amount of ZnO nanosheets can be rapidly prepared at normal temperature and normal pressure through ultrasonic treatment without additionally applying a heat source and pressure in an acid solution.
Example 3
Measuring 9mL concentrated HCl and 3mL concentrated HNO3Forming a mixed solvent in a glass vial, adding 1mmol (183.84mg) of metal nano W powder into the mixed solvent, placing the glass vial in an ultrasonic two-dimensional material stripper (Scientz-CHF-5A, Xinzhi, China) 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, suction filtering, storing the obtained solution for recycling, reducing reagent consumption, washing the obtained yellow powder for 3 times by using 75 v/v% ethanol solution, and finally drying at 80 ℃ for 12h to obtain WO3·H2And (3) an O nanosheet structure. WO obtained by weighing3·H2The mass of the O nano-sheet is 149.91mg, and the yield is 60%.
Example 4
Measuring 36L concentrated HCl and 12L concentrated HNO3Forming a mixed solvent in a wide-mouth glass bottle, adding 10mol (1838.4g) of metal nano W powder into the mixed solvent, placing the wide-mouth glass bottle in an ultrasonic two-dimensional material stripper (Scientz-CHF-5A, New Chinese glossy ganoderma) 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, suction filtering, storing the obtained solution for recycling, reducing reagent consumption, washing the obtained yellow powder for 3 times by using 75 v/v% ethanol solution, and finally drying at 85 ℃ for 12h to obtain WO3·H2And (3) an O nanosheet structure. WO obtained by weighing3The nanosheet mass was 1510.26 g.
FIG. 5(a) shows WO obtained in example 43·H2X-ray diffraction pattern (XRD) of O nanoplatelets. No impurity peak is detected in XRD (X-ray diffraction) spectrum, which indicates that the invention obtains high-purity WO3Nanosheets. While FIG. 5(b) shows WO obtained in example 4 of the present invention3The Raman spectrogram (Raman) shows that the laser excitation wavelength of the test is 532nm, and no impurity peak is detected in the Raman spectrogram, so that the pure WO is obtained3Nanosheets.
FIG. 6 shows WO obtained in example 4 of the present invention3·H2Scanning Electron Microscope (SEM) images of O nanoplates; as can be seen from the figure, the preparation method of the invention obtains WO with large-sheet nanosheet morphology3。WO3The nano-sheet can be formed into a spherical structure by self-assembly with a trend towards more stability for reducing the whole formation.
FIG. 7 shows WO obtained in example 4 of the present invention3·H2High Resolution Transmission Electron Microscopy (HRTEM) images of O nanoplates. Wherein 7(a) shows WO3Is a sheet-like structure, corresponding to the SEM image of FIG. 6; (b) shows that the distance between adjacent crystal planes is measured to be 0.37nm, and WO3The d-spacing values of the medium (120) facets have a good match.
To determine WO3Chemical composition of elements in the nanosheets, X-ray photoelectron spectroscopy (XPS) was performed) FIG. 8 shows WO obtained in example 4 of the present invention3XPS full spectrum energy scan of 0-1200 eV of nanosheets, wherein only W, O element and trace carbon are present, indicating that high purity WO is prepared3Nanosheets.
WO3The synthesis conditions of the nano material are very severe, 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 under normal temperature and normal pressure through ultrasonic treatment without additionally applying heat source and pressure3Nanosheets.
The preparation of WO according to the invention will be explained below3·H2Principle of O nanoplate: first, tungsten powder is oxidized into WO by reaction with aqua regia solution4 2-Then, WO under low pH conditions4 2-Will form WO3·H2And (4) O seed crystal. By ultrasonic treatment, the WO formed3·H2The O nano-particles are used as a seed layer for growth and grow continuously, and dissolved WO4 2-Providing a tungsten source and finally, realizing WO3·H2And (4) growing the O nanosheet.
The ultrasonic preparation method of the nano metal oxide can prepare and obtain products of more than kilogram level at normal temperature and normal pressure, realizes simple, quick and large-scale preparation of the nano metal oxide, and is easy to realize industrial large-scale production.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (20)
1. An ultrasonic preparation method of nano metal oxide is characterized by comprising the following steps: and treating a mixture comprising the simple metal and the acid solution by using ultrasonic waves.
2. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the ultrasonic preparation method is carried out at a temperature of 45 ℃ or less and a pressure of 150KPa or less.
3. The ultrasonic preparation method of nano metal oxide as claimed in 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 nano metal oxide as claimed in claim 1, wherein the acid solution is one of hydrochloric acid solution, acetic acid solution, phosphoric acid solution, sulfuric acid solution, nitric acid solution and aqua regia.
5. The ultrasonic preparation method of nano metal oxide as claimed in claim 4, wherein the concentration of hydrochloric acid solution, acetic acid solution, phosphoric acid solution, sulfuric acid solution and nitric acid solution is not less than 0.1 mol/L.
6. The ultrasonic preparation method of nano metal oxide as claimed in claim 4, wherein the concentration of hydrochloric acid solution, acetic acid solution, phosphoric acid solution, sulfuric acid solution and nitric acid solution is not less than 0.3 mol/L.
7. The ultrasonic preparation method of the nano metal oxide as claimed in claim 1, wherein the metal element is one or more of iron, chromium, cobalt, cadmium, nickel, tin, zinc and tungsten.
8. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the purity of the metal simple substance is not less than 90%.
9. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the purity of the metal simple substance is not less than 95%.
10. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the elementary metal is in bulk or powder form.
11. The ultrasonic preparation method of nanometer metal oxide as claimed in claim 10, wherein when the metal is powder, the average particle diameter of the metal is 5-5000 nm.
12. The ultrasonic preparation method of nanometer metal oxide as claimed in claim 10, wherein when the elementary metal is in powder form, the average particle size of the elementary metal is 10-500 nm.
13. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the ratio of the mass of the metal simple substance to the volume of the acid solution is (0.001-0.3): 1 g/ml.
14. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the mixture comprising the metal simple substance and the acid solution is placed in an ultrasonic instrument for ultrasonic treatment.
15. The ultrasonic preparation method of nano metal oxide as claimed in claim 14, wherein the ultrasonic apparatus is one or more of an ultrasonic cell disruptor, an ultrasonic cleaning machine, and an ultrasonic material stripper.
16. The ultrasonic preparation method of nano metal oxide as claimed in claim 14, wherein the ultrasonic treatment frequency is 20-100KHz and the power is not less than 100W.
17. The ultrasonic preparation method of nano metal oxide as claimed in claim 14, wherein the ultrasonic treatment frequency is 20-50KHz and the power is not less than 200W.
18. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the method is used for preparing nano metal oxide with milligram level or more.
19. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the method is used for preparing nano metal oxide with a kilogram level or more.
20. The ultrasonic preparation method of nano metal oxide as claimed in claim 1, wherein the nano metal oxide is prepared as zero-dimensional, one-dimensional or two-dimensional nano material.
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