CN114524456A - Nano zirconium oxide material and synthetic method thereof - Google Patents

Abstract

The invention discloses a nano-zirconia material and a synthesis method thereof. The nano-zirconia material includes yttrium-doped zirconia nanoparticles; and a zirconia layer wrapping the yttrium-doped zirconia nanoparticles; the synthesis method thereof includes: preparing an aqueous solution A with a yttrium source and a zirconium source; Aqueous solution B is prepared with a volatile substance, and an aqueous solution C is prepared with a zirconium source; the aqueous solution A and the aqueous solution B are added to deionized water to form a first mixed system; the aqueous solution B and the aqueous solution C are added to the first mixed system to form a second mixed system; The second mixed system is subjected to a hydrothermal reaction to obtain a nano-zirconia material; wherein, the pH values of the first mixed system and the second mixed system are both maintained between 8-13. The nano-zirconia material and its synthesis method provided by the present invention are designed so that the yttrium element does not leak out during the cleaning process, so that the tetragonal phase can be maintained in the use environment, the quality of the product is ensured, and the extended period of time is prolonged. usage time.

Description

A kind of nanometer zirconia material and its synthesis method

technical field

The invention belongs to the technical field of fine chemicals and nanometer materials, and particularly relates to a nanometer zirconia material and a synthesis method thereof.

Background technique

Because of its high temperature resistance, corrosion resistance, light weight and high refractive index, nano-zirconia is widely used in the fields of catalysis, batteries, sensors and displays. Nano-zirconia has three phases, namely monoclinic phase, tetragonal phase and cubic phase. The monoclinic phase is the normal temperature phase, and the tetragonal phase and the cubic phase are the high temperature phase. In order to obtain a stable tetragonal phase at room temperature, a common method is to dope other low-valence ions. Among them, yttrium is widely used as a dopant to stabilize tetragonal nano-zirconia due to its non-toxicity, stable chemical properties and low price. Therefore, yttrium-doped nano-zirconia has been widely used in various fields of the industry. The methods of synthesizing nano-zirconia mainly include hydrothermal method and solvothermal method. Among them, the hydrothermal method is cheaper than the solvothermal method, and the use of water as the solvent is more environmentally friendly. Zirconia will produce some by-products in the synthesis process, such as salts such as sodium chloride, and some organic compounds, which will have adverse effects on subsequent use. Therefore, it is necessary to clean the produced nano-zirconia to remove the salts and organics produced in the reaction. However, during the cleaning process, the yttrium element in the yttrium-doped zirconia nanoparticles will seep out, which will cause a phase change in the use environment of the tetragonal zirconia, resulting in a decrease in product performance.

SUMMARY OF THE INVENTION

The main purpose of the present invention is to provide a nano-zirconia material and a synthesis method thereof to overcome the deficiencies in the prior art.

In order to achieve the foregoing purpose of the invention, the technical solutions adopted in the embodiments of the present invention include:

An aspect of an embodiment of the present invention provides a nano-zirconia material, comprising: yttrium-doped zirconia nanoparticles; and a zirconia layer wrapping the yttrium-doped zirconia nanoparticles.

Further, the size of the yttrium-doped zirconia nanoparticles is 5nm-20nm.

Further, the thickness of the zirconia layer is 0.5nm-2nm.

Another aspect of the embodiments of the present invention provides a method for synthesizing a nano-zirconia material, comprising:

Aqueous solution A is prepared with yttrium source and zirconium source, aqueous solution B is prepared with alkaline substance, and aqueous solution C is prepared with zirconium source;

The aqueous solution A and the aqueous solution B are added to deionized water to form a first mixed system;

The aqueous solution B and the aqueous solution C are added to the first mixed system to form a second mixed system;

The second mixed system is subjected to a hydrothermal reaction, and the temperature of the hydrothermal reaction is controlled to be 170°C-240°C to prepare a nano-zirconia material;

Wherein, the pH values of the first mixed system and the second mixed system are both maintained between 8-13.

Further, the total concentration of the yttrium source and the zirconium source in the aqueous solution A is 0.01 mol/L-3 mol/L.

Further, the molar ratio of the yttrium source to the zirconium source in the aqueous solution A is 1%-25%:1.

Further, the concentration of the aqueous solution B is 0.01mol/L-10mol/L.

Further, the concentration of the aqueous solution C is 0.01mol/L-3mol/L.

Further, the method for synthesizing the nano-zirconia material specifically includes: adding the aqueous solution A and the aqueous solution B to the deionized water simultaneously, keeping the pH value of the formed mixed system at 8-13, and after the dripping is completed, The first mixed system is obtained.

Further, the method for synthesizing the nano-zirconia material specifically includes: adding the aqueous solution B and the aqueous solution C dropwise to the first mixed system simultaneously, keeping the pH value of the formed mixed system at 8-13, and finishing the dropwise addition. Afterwards, the second mixed system is obtained.

Another aspect of the embodiments of the present invention also provides a nano-zirconia material, which is prepared by the above method.

Compared with the prior art, the present invention has the following beneficial effects:

The nano zirconia material and the synthesis method of the present invention, through the improvement of the synthesis method and the design of the nanostructure, greatly reduce the exudation ratio of yttrium in the cleaning process, ensure the stability of the tetragonal phase, and prolong the Product life.

Description of drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only These are some embodiments described in this application. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

FIG. 1 is a schematic structural diagram of zirconia in an embodiment of the present application.

FIG. 2 is an X-ray diffraction (XRD) pattern of the zirconia obtained in Example 1. FIG.

3 is an X-ray diffraction (XRD) pattern of the zirconia obtained in Example 1 after annealing in a humid environment of 100° C. for 48 hours.

FIG. 4 is an X-ray diffraction (XRD) pattern of the zirconia obtained in Comparative Example 1. FIG.

FIG. 5 is an X-ray diffraction (XRD) pattern of the zirconia obtained in Comparative Example 1 after annealing in a humid environment of 100° C. for 48 hours.

DESCRIPTION OF REFERENCE NUMERALS: 1. Yttrium-doped zirconia nanoparticles, 2. zirconia layer.

Detailed ways

An aspect of this embodiment provides a nano-zirconia material, comprising: yttrium-doped zirconia nanoparticles; and a zirconia layer wrapping the yttrium-doped zirconia nanoparticles.

In some preferred embodiments, the yttrium-doped zirconia nanoparticles are tetragonal.

In some preferred embodiments, the size of the yttrium-doped zirconia nanoparticles is 5 nm-20 nm.

In some preferred embodiments, the thickness of the zirconia layer is 0.5nm-2nm.

Another aspect of the embodiments of the present invention provides a method for synthesizing a nano-zirconia material, comprising:

Aqueous solution A is prepared with yttrium source and zirconium source, aqueous solution B is prepared with alkaline substance, and aqueous solution C is prepared with zirconium source;

The aqueous solution A and the aqueous solution B are added to deionized water to form a first mixed system;

The aqueous solution B and the aqueous solution C are added to the first mixed system to form a second mixed system;

The second mixed system is subjected to a hydrothermal reaction, and the temperature of the hydrothermal reaction is controlled to be 170°C-240°C to prepare a nano-zirconia material;

Wherein, the pH values of the first mixed system and the second mixed system are both maintained between 8-13.

In some preferred embodiments, the total concentration of the yttrium source and the zirconium source in the aqueous solution A is 0.01 mol/L-3 mol/L.

In some more preferred embodiments, the molar ratio of the yttrium source to the zirconium source in the aqueous solution A is 1%-25%:1.

In some preferred embodiments, the concentration of the aqueous solution B is 0.01 mol/L-10 mol/L.

In some preferred embodiments, the concentration of the aqueous solution C is 0.01 mol/L-3 mol/L.

In some more preferred embodiments, the yttrium source may include any one or a combination of yttrium chloride, yttrium nitrate, yttrium oxide, etc., but is not limited thereto.

In some more preferred embodiments, the zirconium source may include, but is not limited to, any one or a combination of any of zirconium oxychloride, zirconium oxynitrate, and the like.

In some more preferred embodiments, the alkaline substance can include any one or a combination of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., But not limited to this.

In some preferred embodiments, the method for synthesizing the nano-zirconia material specifically includes: adding aqueous solution A and aqueous solution B to deionized water simultaneously, keeping the pH value of the formed mixed system at 8-13, dropping After the addition is completed, the first mixed system is obtained.

In some preferred embodiments, the method for synthesizing the nano-zirconia material specifically includes: adding the aqueous solution B and the aqueous solution C dropwise to the first mixed system at the same time, and keeping the pH value of the formed mixed system at 8-13 , and after the dropwise addition is completed, the second mixed system is obtained.

Another aspect of the embodiments of the present invention also provides a nano-zirconia material, which is prepared by the above method.

The technical solutions in the embodiments of the present invention will be described in detail below with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

Example 1

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, which is called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain a nano-zirconia material, as shown in FIG. Heterozirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.55 nm.

Example 2

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, called solution A, wherein yttrium chloride accounts for 12% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain a nano-zirconia material. As shown in FIG. 1 , the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 7.2 nm and a coated yttrium zirconia material. A zirconia layer 2 with a thickness of 0.52 nm is doped with zirconia nanoparticles 1 .

Example 3

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, called solution A, wherein yttrium chloride accounts for 25% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain a nano-zirconia material. As shown in FIG. 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 7.5 nm and a coated yttrium zirconia material. A zirconia layer 2 with a thickness of 0.51 nm is doped with zirconia nanoparticles 1 .

Example 4

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, which is called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 24ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=13. After the dropwise addition, the first mixed system was obtained.

Afterwards, measure 1 ml of solution C and 2.3 ml of solution B, and add them dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=13. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in FIG. 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 5 nm and wrapped yttrium-doped zirconia nanoparticles 1. Zirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.7 nm.

Example 5

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01mol/L, called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 16ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=10. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1 ml of solution C and 2.3 ml of solution B, and add them dropwise into the first mixed system simultaneously at a certain speed, keeping the pH value of the formed mixed system=10. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in Figure 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 6 nm and a wrapped yttrium-doped zirconia. Zirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.9 nm.

Example 6

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, which is called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 240°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in Figure 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 6.5 nm and wrapped yttrium-doped zirconia nanoparticles 1. Heterozirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 1.1 nm.

Example 7

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, which is called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 200°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in FIG. 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 6.8 nm and wrapped yttrium-doped zirconia nanoparticles 1. Heterozirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 1 nm.

Example 8

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, which is called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 16h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in FIG. 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 10 nm and a wrapped yttrium-doped zirconia. Zirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.5 nm.

Example 9

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 24h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in FIG. 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 12 nm and wrapped yttrium-doped zirconia. Zirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.5 nm.

Example 10

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, which is called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 2ml of solution C and 4.6ml of solution B, and add them dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia, as shown in FIG. Zirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 1 nm.

Example 11

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, which is called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 4ml of solution C and 9.2ml of solution B, and add them dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in Figure 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 7 nm and a wrapped yttrium-doped zirconia. Zirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 2 nm.

Example 12

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 3 mol/L, which is called solution A, in which yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; Sodium hydroxide is configured into a 10 mol/L solution, which is called solution B; zirconium oxychloride is configured into a 3 mol/L solution, which is called solution C.

5ml of A solution and 3.6ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 4ml of solution C and 2.7ml of solution B, and add them dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system = 8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in Figure 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 20 nm and wrapped yttrium-doped zirconia nanoparticles 1. Zirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 1 nm.

Example 13

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 1 mol/L, which is called solution A, in which yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; Sodium hydroxide is configured into a 1mol/L solution, which is called solution B; zirconium oxychloride is configured into a 1mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

After that, measure 4ml of solution C and 9.2ml of solution B, and add them dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain nano-zirconia. As shown in FIG. 1, the nano-zirconia material includes yttrium-doped zirconia nanoparticles 1 with a particle size of 10 nm and wrapped yttrium-doped zirconia nanoparticles 1. Zirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 2 nm.

Example 14

Yttrium nitrate and zirconium oxynitrate are configured into a solution with a total concentration of yttrium nitrate and zirconium oxynitrate of 0.01 mol/L, called solution A, in which yttrium nitrate accounts for 1% of the molar ratio of zirconium oxynitrate; potassium hydroxide is configured as The solution of 0.01mol/L is called solution B; the solution of zirconium oxychloride configured as 0.01mol/L is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain a nano-zirconia material, as shown in FIG. Heterozirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.55 nm.

Example 15

Yttrium oxide and zirconium oxynitrate are configured into a solution with a total concentration of yttrium oxide and zirconium oxynitrate of 0.01 mol/L, called solution A, in which yttrium oxide accounts for 1% of the molar ratio of zirconium oxynitrate; potassium hydroxide is configured as The solution of 0.01mol/L is called solution B; the solution of zirconium oxychloride configured as 0.01mol/L is called solution C.

5ml of solution A and 12ml of solution B were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain a nano-zirconia material, as shown in FIG. Heterozirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.55 nm.

Example 16

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, which is called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The tetramethylammonium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain a nano-zirconia material, as shown in FIG. Heterozirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.55 nm.

Example 17

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, called solution A, in which yttrium oxide accounts for 1% of the molar ratio of zirconium oxychloride; The solution of tetraethylammonium hydroxide is set to 0.01mol/L, which is called solution B; the solution of zirconium oxychloride is set to 0.01mol/L, which is called solution C.

5ml of A solution and 12ml of B solution were simultaneously added dropwise to 5ml of deionized water at a certain speed to keep the pH value of the formed mixed system=8. After the dropwise addition, a first mixed system was obtained.

Afterwards, measure 1ml of solution C and 2.3ml of solution B, dropwise into the first mixed system simultaneously at a certain speed, and continue to maintain the pH value of the formed mixed system=8. After the dropwise addition, a second mixed system is obtained.

Then, the second mixed system was poured into the reaction kettle for hydrothermal reaction, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction is completed, it is cooled to room temperature, centrifuged, washed, dried, and collected to obtain a nano-zirconia material, as shown in FIG. Heterozirconia nanoparticles 1, and a zirconia layer 2 with a thickness of 0.55 nm.

Comparative Example 1

Yttrium chloride and zirconium oxychloride are configured into a solution with a total concentration of yttrium chloride and zirconium oxychloride of 0.01 mol/L, called solution A, wherein yttrium chloride accounts for 1% of the molar ratio of zirconium oxychloride; The sodium hydroxide is configured into a 0.01 mol/L solution, which is called solution B; the zirconium oxychloride is configured into a 0.01 mol/L solution, which is called solution C.

5ml of A solution and 12ml of B solution were added dropwise to 5ml of deionized water at a certain speed at the same time, maintaining the pH value of the formed mixed system=8, after the dropwise addition, a mixed system was obtained, and the above mixed system was poured into the reaction The hydrothermal reaction was carried out in the kettle, the reaction temperature was 170°C, and the reaction time was 6h. After the reaction, it was cooled to room temperature, centrifuged, washed, dried, and collected to obtain zirconia.

The zirconia obtained in Example 1 and Comparative Example 1 were respectively subjected to X-ray diffraction analysis and X-ray diffraction analysis after annealing in a humid environment of 100° C. for 48 hours. The analysis results are shown in Figures 2-5.

It can be seen from Figure 2 that the XRD diffraction peak of the zirconia nanomaterial synthesized in Example 1 has a strong diffraction peak when 2θ is 30.5°, indicating that the synthesized nanomaterial has a tetragonal phase. After annealing in a humid environment of 100° C. for 48 hours, it can be seen from FIG. 3 that the zirconia nanomaterial synthesized in Example 1 still has a tetragonal phase structure. It can be seen from Figure 4 that although the phase of the zirconia nanomaterial synthesized in Comparative Example 1 is a tetragonal phase, the position of the diffraction peak is obviously shifted after annealing in a humid environment of 100 °C for 48 h. From the tetragonal phase to the monoclinic phase. It can be seen that the zirconia nanomaterial synthesized in Example 1 has better stability than the nanomaterial synthesized in the comparative example.

In addition, the inventors of the present application also carried out experiments with other raw materials, technological operations and technological conditions mentioned in this specification with reference to the foregoing examples, and all obtained satisfactory results.

Although the present invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions and/or additions and the like may be made without departing from the spirit and scope of the invention Effects replace elements of the described embodiments. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is not intended herein to limit the invention to the particular embodiments disclosed for carrying out the invention, but it is intended that this invention include all embodiments falling within the scope of the appended claims. Furthermore, unless specifically stated, any use of the terms first, second, etc. does not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (10)

1. A nano zirconia material, comprising: yttrium-doped zirconia nanoparticles; and a zirconia layer encasing the yttrium-doped zirconia nanoparticles.

2. The nano zirconia material of claim 1, wherein: the yttrium-doped zirconia nanoparticles are tetragonal.

3. The nanozirconia material of claim 1 or 2, wherein: the size of the yttrium-doped zirconia nano-particles is 5nm-20nm, and/or the thickness of the zirconia layer is 0.5nm-2 nm.

4. A method for synthesizing a nano zirconia material is characterized by comprising the following steps:

preparing an aqueous solution A by using an yttrium source and a zirconium source, preparing an aqueous solution B by using an alkaline substance, and preparing an aqueous solution C by using a zirconium source;

adding the aqueous solution A and the aqueous solution B into deionized water to form a first mixed system;

adding the aqueous solution B and the aqueous solution C into the first mixed system to form a second mixed system;

carrying out hydrothermal reaction on the second mixed system, and controlling the temperature of the hydrothermal reaction to be 170-240 ℃ to prepare a nano zirconia material;

wherein the pH values of the first mixed system and the second mixed system are both kept between 8 and 13.

5. The method for synthesizing nano zirconia material according to claim 4, wherein: the total concentration of the yttrium source and the zirconium source in the aqueous solution A is 0.01-3 mol/L; and/or the molar ratio of the yttrium source to the zirconium source in the aqueous solution A is 1-25%: 1; and/or the concentration of the aqueous solution B is 0.01-10 mol/L; and/or the concentration of the aqueous solution C is 0.01mol/L-3 mol/L.

6. The method for synthesizing nano zirconia material according to claim 4, wherein: the yttrium source comprises any one or more of yttrium chloride, yttrium nitrate and yttrium oxide, and/or the zirconium source comprises any one or more of oxychlorination and zirconyl nitrate, and/or the alkaline substance comprises any one or more of sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide.

7. The method for synthesizing the nano zirconia material according to claim 5, which specifically comprises: and (3) simultaneously dropwise adding the aqueous solution A and the aqueous solution B into deionized water, keeping the pH value of the formed mixed system at 8-13, and obtaining the first mixed system after dropwise adding.

8. The method for synthesizing the nano zirconia material according to claim 7, specifically comprising: and (3) simultaneously dropwise adding the aqueous solution B and the aqueous solution C into the first mixed system, keeping the pH value of the formed mixed system at 8-13, and obtaining the second mixed system after dropwise adding.

9. The method for synthesizing nano zirconia material according to claim 4, wherein: the time of the hydrothermal reaction is 6-16 h.

10. A nano zirconia material produced by the method of any one of claims 4 to 9.

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