CN108298502B - A kind of method for preparing dispersed nanometer metal oxide and nanometer metal powder - Google Patents
A kind of method for preparing dispersed nanometer metal oxide and nanometer metal powder Download PDFInfo
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Abstract
本发明公开了一种制备分散纳米金属氧化物及纳米金属粉的方法，将金属硫酸盐和硫酸钾混合溶液在弱极性有机溶剂中沉淀，同时使用聚丙烯酸作为形核剂，在沉淀物中形成纳米硫酸钾颗粒分散隔离纳米硫酸盐颗粒的状态。将沉淀物烘干后进行高温煅烧分解，该金属硫酸盐分解成金属氧化物，而硫酸钾颗粒始终起到隔离作用。水洗后可得到分散的纳米金属氧化物。将煅烧产物在还原气氛中二次煅烧，水洗后可得分散的纳米金属粉。本发明可以快速批量制备出分散性好、结晶完善的纳米金属氧化物或纳米金属粉。
The invention discloses a method for preparing dispersed nanometer metal oxide and nanometer metal powder. The mixed solution of metal sulfate and potassium sulfate is precipitated in a weakly polar organic solvent, and polyacrylic acid is used as a nucleating agent at the same time. A state in which the nano-potassium sulfate particles are dispersed and isolated from the nano-sulfate particles is formed. After the precipitate is dried and decomposed by high temperature calcination, the metal sulfate is decomposed into metal oxide, and the potassium sulfate particles always play a role in isolation. Dispersed nano metal oxides can be obtained after washing with water. The calcined product is calcined for a second time in a reducing atmosphere, and after washing with water, dispersed nanometer metal powder can be obtained. The invention can quickly and batch prepare nanometer metal oxides or nanometer metal powders with good dispersibility and perfect crystallization.
Description
Technical Field
The invention relates to a technology for preparing dispersed nano metal oxide and nano metal powder, belonging to the field of nano powder preparation.
Background
The nano metal oxide has surface effect, quantum size effect, volume effect and macroscopic quantum tunnel effect, so that the nano metal oxide has unique thermal, optical, electrical, magnetic and chemical properties and is widely applied to the fields of electronics, chemical engineering, machinery, biomedicine and the like.
However, the nano metal oxide is easy to agglomerate and sinter during the preparation process, so that it is difficult to prepare dispersed nano particles. At present, liquid phase methods are widely adopted in industry and laboratories to prepare nano metal oxides, firstly nano metal oxide precursors such as hydroxides, oxalates, carbonates and the like are synthesized in solution, and then the precursors are calcined and decomposed at high temperature to obtain the nano metal oxides. The calcination decomposition temperature is often higher, for example, 350 ℃ is needed for magnesium carbonate decomposition, 500 ℃ is needed for completely converting ferric hydroxide into ferric oxide, and 1000 ℃ is needed for obtaining alpha-phase alumina. At such high temperatures, agglomeration and sintering of the metal oxide nanoparticles are difficult to avoid. So far, only iron oxide and zinc oxide can be used to prepare monodisperse nanoparticles by hydrothermal method or forced hydrolysis method, and the efficiency is low. For other metal oxides which need to be calcined at high temperature, the prior art is difficult to prepare nano powder with high dispersibility on a large scale.
One possible approach to solving this problem is: high-melting-point water-soluble inorganic salt is used as an isolation phase to prevent agglomeration and sintering of metal oxide nanoparticles, so that the nanoparticles are always isolated by solid salt in a dispersing manner in a high-temperature process, and the inorganic salt is washed away after calcination to obtain dispersed metal oxide nanoparticles. However, the key problem of this method is how to obtain water-soluble salt particles at the nano-scale and effectively isolate and disperse the precursor nanoparticles with the nano-salt particles. Commercial water solubility such as NaCl (melting point 801 ℃), K2SO4Particles (melting point 1067 ℃ C.) and the like are generally about several tens of micrometers, and the nano-scale precursor particles cannot be isolated by such coarse particles. It is also difficult to reduce the size of the salt particles to the nano-scale by ball milling or the like. In the earlier stage of the subject group, a salt shell is coated on the surface of the nano-particles by using a salt-containing micro-emulsion method (Chinese patent 201610365324.4), and finally, monodisperse nano-oxide particles are prepared. However, the method has high raw material cost and complicated working procedures, and is not suitable for large-scale production.
In summary, the agglomeration and sintering of metal oxide nanoparticles during the high-temperature calcination decomposition process are difficult to avoid during the preparation process, and the prior art is difficult to solve the problem. The use of high melting water soluble inorganic salts to isolate the precursor particles is one possible approach to solve this problem, but provided that dispersion and isolation of the precursor nanoparticles from the soluble salts must be achieved. If the size of the high-melting-point inorganic salt particles can be reduced to the nanometer level and the inorganic salt nanoparticles are used for dispersing the precursor nanoparticles, the problems of agglomeration and sintering of the metal oxide nanoparticles in the high-temperature calcination process can be effectively solved, and the high-dispersity metal oxide nanoparticles can be prepared.
Disclosure of Invention
The technical problem is as follows: the invention provides a method for rapidly preparing nano metal oxide and nano metal powder in batches, nano particles with the particle size of less than 100nm can be stably prepared, the prepared nano metal oxide has good crystallinity, and the prepared nano metal powder has perfect crystallization, and good conductivity and magnetic performance.
The technical scheme is as follows: the method for preparing the dispersed nano metal oxide comprises the following steps:
1) preparing a mixed aqueous solution of sulfate corresponding to the metal oxide and potassium sulfate;
2) adding polyacrylic acid into the mixed aqueous solution prepared in the step 1);
3) under the condition of stirring, dripping a mixed aqueous solution containing polyacrylic acid into an organic solvent to obtain a precipitate;
4) washing the precipitate with organic solvent for 1-2 times, and drying to obtain nanometer sulfate mixture;
5) calcining the mixture of nano-sulfates below the melting point of potassium sulfate;
6) washing and drying the calcined product obtained in the step 5) by using water to obtain the nano metal oxide.
Further, in the method for preparing a dispersed nano metal oxide according to the present invention, in the step 1), the metal oxide is aluminum oxide, titanium oxide, iron oxide, nickel oxide, cobalt oxide, copper oxide, magnesium oxide, zirconium oxide, cadmium oxide, tin oxide, zinc oxide, indium oxide, yttrium oxide, europium oxide, cerium oxide, lanthanum oxide, terbium oxide, dysprosium oxide, or neodymium oxide.
Further, in the method for preparing the dispersed nano metal oxide, in the step 1), the molar ratio of the potassium sulfate to the metal sulfate is not less than 1: 1, and the concentration of the potassium sulfate in the prepared mixed aqueous solution is 0.01mol/L to saturation.
Further, in the method for preparing the dispersed nano metal oxide, the adding amount of the polyacrylic acid in the step 2) is 0.5-100% of the total mass of the sulfate.
Further, in the method for preparing a dispersed nano metal oxide according to the present invention, the organic solvent in step 3) is methanol, ethanol, tert-butanol, acetone or dimethylformamide, and the organic solvent in step 4) is methanol, ethanol, tert-butanol, acetone or dimethylformamide.
The method for preparing the dispersed nano metal powder comprises the following steps:
1) preparing a mixed aqueous solution from sulfate corresponding to metal and potassium sulfate;
2) adding polyacrylic acid into the mixed aqueous solution prepared in the step 1);
3) under the condition of stirring, dripping a mixed aqueous solution containing polyacrylic acid into an organic solvent to obtain a precipitate;
4) washing the precipitate with organic solvent for 1-2 times, and drying to obtain nanometer sulfate mixture;
5) calcining the mixture of nano-sulfates below the melting point of potassium sulfate;
6) and (3) carrying out secondary calcination on the calcined product obtained in the step 5) in a reducing atmosphere, cooling, washing with water, and drying to obtain the nano metal powder.
Further, in the method for preparing dispersed nano metal powder of the present invention, in the step 1), the metal is iron, nickel, cobalt or copper.
Further, in the method for preparing the dispersed nano metal powder, in the step 1), the molar ratio of the potassium sulfate to the metal sulfate is not less than 1: 1, and the concentration of the potassium sulfate in the prepared mixed aqueous solution is 0.01mol/L to saturation.
Further, in the method for preparing the dispersed nano metal powder, the adding amount of the polyacrylic acid in the step 2) is 0.5-100% of the total mass of the sulfate.
Further, in the method for preparing dispersed nano metal powder of the present invention, the organic solvent in step 3) is methanol, ethanol, tert-butanol, acetone or dimethylformamide, and the organic solvent in step 4) is methanol, ethanol, tert-butanol, acetone or dimethylformamide.
In the invention, a mixed sulfate aqueous solution is prepared by a certain metal sulfate and potassium sulfate, and polyacrylic acid with the mass of more than 0.5 percent of sulfate is added into the mixed sulfate aqueous solution. When the mixed sulfate aqueous solution is dripped into the organic solvent, mixed precipitates of the sulfate nanoparticles and the potassium sulfate nanoparticles are separated out, and the isolated state of the potassium sulfate nanoparticles to the sulfate nanoparticles is formed. During the subsequent calcination process, the metal sulfate is decomposed into metal oxide, while the potassium sulfate is unchanged and plays a role of isolation all the time.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the existing methods for preparing nano metal oxides, such as chemical precipitation method, sol-gel method, etc., generally prepare precursors, such as metal carbonates or hydroxides, etc., and then calcine at high temperature to decompose into metal oxides. However, the smaller the particle size, the larger the surface energy and the easier it is to agglomerate. In both the dehydration drying process and the high-temperature calcination process, the metal oxide particles are inevitably agglomerated, and sintering occurs between the particles at high temperature, so that it is difficult to prepare highly dispersed nano metal oxide particles.
The isolated phase can prevent agglomeration and sintering of precursor particles, and at present, most of the isolated phases are researched to contain carbon, water-soluble inorganic salt and the like. The residual carbon of the carbon isolation method is difficult to remove, and the performance of the nano particles is greatly influenced. The water-soluble inorganic salt isolation method has a good isolation effect theoretically, is easy to clean and clear by water washing, and is simple and easy to implement. However, the particle size of the water-soluble inorganic salt is often large, for example, the particle size of NaCl is often more than tens of micrometers, and it is difficult to effectively disperse and isolate the nano-scale precursor particles with such large salt particles. Therefore, the key problem of using high melting point water-soluble salt as the isolated phase is to prepare nano-scale water-soluble salt particles and effectively isolate and disperse precursor nanoparticles by using the nano-salt particles.
The invention utilizes the characteristic that the solubility of the sulfate in a weak polar organic solvent is greatly reduced to separate out the sulfate particles from the organic solvent, but the size of the sulfate particles obtained in the prior art is in micron order. The polyacrylic acid can be used as a nucleating agent of sulfate, and after the polyacrylic acid is added into the mixed sulfate solution, the nucleating rate can be greatly improved, and the size of sulfate particles can be reduced. When polyacrylic acid with the mass of sulfate more than 0.5 percent is added, the size of sulfate particles can be effectively reduced to be less than 100 nm.
The action mechanism of polyacrylic acid is not clear at present, and the concept of nucleating agent does not exist in the technical field of organic solvent precipitation method. In the field of metal solidification, the nucleating agent is solid particles and can be used as a nucleating substrate during metal solidification, so that the nucleating rate is greatly improved, and the grain size is reduced. Polyacrylic acid is a water-soluble polymer material, and the action mechanism of polyacrylic acid is obviously greatly different from that of a solid nucleating agent in the solidification process. The effect of polyacrylic acid in promoting the nucleation of potassium sulfate in the present invention is unpredictable from the prior art knowledge.
The invention prepares the sulfate corresponding to the metal oxide (or metal powder) to be prepared and potassium sulfate into mixed sulfate aqueous solution, and adds polyacrylic acid with the sulfate mass of more than 0.5 percent into the mixed sulfate aqueous solution. When the mixed sulfate aqueous solution is dripped into the organic solvent, mixed precipitates of the sulfate nanoparticles and the potassium sulfate nanoparticles are separated out, and the isolated state of the potassium sulfate nanoparticles to the sulfate nanoparticles is formed.
Taking a mixed solution of nickel sulfate and potassium sulfate as an example, when the molar ratio of potassium sulfate to nickel sulfate exceeds 1: 1, adding the mixed solution into an organic solvent such as ethanol and the like to obtain a mixed nano sulfate precipitate, wherein the precipitate can form a state that nano potassium sulfate particles are dispersed and isolated from nano nickel sulfate particles, as shown in the attached figure 1 of the specification. In the subsequent high-temperature calcination process, the nano nickel sulfate is decomposed to generate nano nickel oxide, and the nano potassium sulfate is not decomposed. In the process of generating the nano nickel oxide, the nano nickel oxide is dispersed and isolated by the solid particles of the nano potassium sulfate all the time, so that agglomeration and sintering cannot occur, and the dispersed nano nickel oxide can be obtained after the potassium sulfate is removed by washing, as shown in the attached figure 2 of the specification. And if the calcined product is calcined for the second time in a reducing atmosphere, the dispersed nano nickel powder can be obtained after washing.
If the dispersant is added into the organic solvent, the isolating effect of the nanometer potassium sulfate can be further improved. The dispersant includes polyethylene glycol, polyvinylpyrrolidone, carboxylic acid surfactant, etc.
The invention can rapidly prepare the nano metal oxide with good dispersibility in batches, solves the agglomeration and sintering problems of the nano metal oxide, and has good crystallinity of the prepared nano metal oxide because the calcining temperature can reach more than 1000 ℃. For the same reason, the nano metal powder prepared by the invention has perfect crystallization and good conductivity and magnetic property.
The reagents used in the method are all common cheap reagents, and the method is simple and convenient and is easy for large-scale production.
Drawings
FIG. 1 is the scanning electron microscope image of the mixture of nanometer nickel sulfate and nanometer potassium sulfate.
FIG. 2 shows the preparation of nano nickel oxide at 1000 deg.C.
Detailed Description
The invention is further described with reference to the following examples and the accompanying drawings.
Example 1: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the aluminum sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of sulfate is added, and the solution is clear. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 2: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.1mol/L, the concentration of the aluminum sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 3: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.01mol/L, the concentration of the aluminum sulfate is 0.03mol/L, polyacrylic acid with 5 percent of the total mass of sulfate is added, and the solution is clear. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 4: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.01mol/L, the concentration of the aluminum sulfate is 0.05mol/L, polyacrylic acid with 5 percent of the total mass of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 5: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.57mol/L (saturated), the concentration of the aluminum sulfate is 0.05mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is clear. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 6: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the aluminum sulfate is 0.1mol/L, polyacrylic acid with the total mass of 0.5 percent of sulfate is added, and the solution is clear. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 7: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the aluminum sulfate is 0.1mol/L, polyacrylic acid with the total mass of 10% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 8: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.02mol/L, the concentration of the aluminum sulfate is 0.01mol/L, polyacrylic acid with 100 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 11: deionized water is used for preparing 10 ml of mixed solution of titanium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the titanium sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano titanium oxide.
Example 12: deionized water is used for preparing 10 ml of mixed solution of ferric sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the ferric sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano iron oxide.
Example 13: deionized water is used for preparing 10 ml of mixed solution of nickel sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the nickel sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano nickel oxide.
Example 14: deionized water is used for preparing 10 ml of mixed solution of cobalt sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the cobalt sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano cobalt oxide.
Example 15: deionized water is used for preparing 10 ml of mixed solution of copper sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the copper sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano copper oxide.
Example 16: deionized water is used for preparing 10 ml of mixed solution of magnesium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the magnesium sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-magnesium oxide.
Example 17: deionized water is used for preparing 10 ml of mixed solution of zirconium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the zirconium sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-zirconia.
Example 18: deionized water is used for preparing 10 ml of mixed solution of cadmium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the cadmium sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5 percent of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano cadmium oxide.
Example 19: deionized water is used for preparing 10 ml of mixed solution of tin sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the tin sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano tin oxide.
Example 20: deionized water is used for preparing 10 ml of mixed solution of zinc sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the zinc sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano zinc oxide.
Example 21: deionized water is used for preparing 10 ml of mixed solution of indium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the indium sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano indium oxide.
Example 22: deionized water is used for preparing 10 ml of mixed solution of yttrium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the yttrium sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano yttrium oxide.
Example 23: deionized water is used for preparing 10 ml of mixed solution of europium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the europium sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano europium oxide.
Example 24: deionized water is used for preparing 10 ml of mixed solution of cerium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the cerium sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano cerium oxide.
Example 25: deionized water is used for preparing 10 ml of mixed solution of lanthanum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the lanthanum sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano lanthanum oxide.
Example 26: deionized water is used for preparing 10 ml of mixed solution of terbium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the terbium sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano terbium oxide.
Example 27: preparing 10 ml of mixed solution of dysprosium sulfate and potassium sulfate by using deionized water, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the dysprosium sulfate is 0.1mol/L, adding polyacrylic acid with the total mass of 5% of sulfate, and dissolving the polyacrylic acid clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano dysprosium oxide.
Example 28: deionized water is used for preparing 10 ml of mixed solution of neodymium sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the neodymium sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano neodymium oxide.
Example 29: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the aluminum sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of sulfate is added, and the solution is clear. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of methanol under stirring, washing the precipitate with methanol for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 30: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the aluminum sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of sulfate is added, and the solution is clear. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of tertiary butanol under the condition of stirring, washing the precipitate for 1 time by using the tertiary butanol, drying, calcining at 1000 ℃, cooling, washing by using water, and drying to obtain the dispersed nano-alumina.
Example 31: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the aluminum sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of sulfate is added, and the solution is clear. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of acetone under stirring, washing the precipitate with acetone for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 32: deionized water is used for preparing 10 ml of mixed solution of aluminum sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the aluminum sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of sulfate is added, and the solution is clear. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of dimethyl formamide under stirring, washing the precipitate with dimethyl formamide for 1 time, drying, calcining at 1000 ℃, cooling, washing with water, and drying to obtain the dispersed nano-alumina.
Example 33: deionized water is used for preparing 10 ml of mixed solution of ferric sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the ferric sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, carrying out secondary calcination on the calcined product in a reducing atmosphere, cooling, washing with water, and drying to obtain the nano metal iron powder.
Example 34: deionized water is used for preparing 10 ml of mixed solution of nickel sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the nickel sulfate is 0.1mol/L, polyacrylic acid with the total mass of 5% of sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml ethanol under stirring, washing precipitate with ethanol for 1 time, drying, calcining at 1000 deg.C, calcining the calcined product in reducing atmosphere for two times, cooling, washing with water, and drying to obtain nanometer nickel powder
Example 35: deionized water is used for preparing 10 ml of mixed solution of cobalt sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the cobalt sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate with ethanol for 1 time, drying, calcining at 1000 ℃, carrying out secondary calcination on the calcined product in a reducing atmosphere, cooling, washing with water, and drying to obtain nano metal cobalt powder
Example 36: deionized water is used for preparing 10 ml of mixed solution of copper sulfate and potassium sulfate, wherein the concentration of the potassium sulfate is 0.2mol/L, the concentration of the copper sulfate is 0.1mol/L, polyacrylic acid with 5 percent of the total mass of the sulfate is added, and the solution is dissolved clearly. Dropping mixed sulfate solution containing polyacrylic acid into 50 ml of ethanol under the condition of stirring, washing the precipitate for 1 time by using the ethanol, drying, calcining at 1000 ℃, carrying out secondary calcination on the calcined product in a reducing atmosphere, cooling, washing by using water, and drying to obtain the nano metal copper powder.
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| WO2021168736A1 (en) * | 2020-02-27 | 2021-09-02 | 东南大学 | Method for preparing tetragonal-phase barium titanate nanoparticle |
| CN111320193B (en) * | 2020-02-27 | 2023-12-29 | 东南大学 | Metal oxide nanoparticle and method for producing metal nanoparticle |
| CN115231614B (en) * | 2022-04-25 | 2024-04-19 | 东南大学 | Preparation method of yttrium-doped zirconium oxide nanoparticles |
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