CN113511688A

CN113511688A - FeVO4Preparation method of hollow sphere

Info

Publication number: CN113511688A
Application number: CN202110982169.1A
Authority: CN
Inventors: 曾毅; 王贺楠; 乔靓
Original assignee: Hangzhou Hengyi Zhichuang Technology Co ltd
Current assignee: Hangzhou Hengyi Zhichuang Technology Co ltd
Priority date: 2021-08-25
Filing date: 2021-08-25
Publication date: 2021-10-19
Anticipated expiration: 2041-08-25

Abstract

The invention discloses a FeVO₄The preparation method of the hollow sphere comprises the following steps: (1) preparing a carbon sphere template: adding glucose into deionized water, stirring and mixing uniformly, adding ammonia water in the stirring process to adjust the pH value to 9-12, then carrying out hydrothermal reaction, and then washing, filtering and drying to obtain carbon spheres; (2) preparing a precursor: dispersing carbon spheres in absolute ethyl alcohol, and then adding FeCl₂And VCl₃Stirring, mixing, standing for 24-48h, washing, filtering, and drying to obtain precursor; (3) and (3) calcining: the precursor is calcined at high temperature and cooled to obtain FeVO₄The hollow ball. The method has the advantages of simple and easy process, low cost, environmental protection and no pollution, and can obtain products with better appearance.

Description

FeVO4Preparation method of hollow sphere

Technical Field

The invention relates to the technical field of functional material production, in particular to FeVO₄A preparation method of hollow spheres.

Background

In recent years, the nano material with the appearance of hollow spheres is receiving more and more attention. The application range is very wide, and the method covers various fields including: gas sensors, photocatalysts, supercapacitors, and the like. The synthesis method of the hollow nanospheres is various and is generally simpler, and the application range of the hollow nanospheres in various industries is further popularized. Currently common synthetic methods include hard template methods, soft template methods, and self-templating methods. Among them, the hard template method is the most effective method for preparing the hollow structure. The hard template method can generally synthesize a material with excellent morphology efficiently, but collapse and damage of a shell layer easily occur in the process of removing the template, so that the morphology is deteriorated, the synthesis of the template plays a decisive role in the synthesis of a subsequent target material, and once the morphology of the template has a large defect, the morphology of a final sample is also poor. Therefore, the method has extremely important significance for exploring the sample with excellent appearance prepared by the hard template method.

Iron and vanadium are two elements which are very common in daily life and industrial production, and are very cheap. The iron vanadium oxide also has very excellent performance. FeVO₄Is an N-type semiconductor, and has attracted wide attention because of its narrow band gap, stable chemical properties and cheap raw materials. For example, in the photocatalytic context, FeVO₄Has good photocatalytic activity and simultaneously FeVO₄Is also an excellent electrode material for lithium batteries.

However, FeVO is currently prepared₄Most of the methods can not achieve the purpose of randomly controlling the appearance, and most of the methods can not prepare samples with better appearance. In addition, most preparation methods adopt ammonium metavanadate as a raw material, and the solubility of the material is very low, so that the preparation difficulty is undoubtedly increased, and a better appearance is difficult to form. Therefore, the development of a preparation method of the FeVO4 hollow sphere is of great significance.

Disclosure of Invention

The invention aims to provide FeVO₄The preparation method of the hollow sphere has the advantages of simple and feasible process, low cost, environmental protection and no pollution, and can obtain products with better appearance.

The technical scheme adopted by the invention for solving the technical problems is as follows:

FeVO₄The preparation method of the hollow sphere comprises the following steps:

(1) preparing a carbon sphere template: adding glucose into deionized water, stirring and mixing uniformly, adding ammonia water in the stirring process to adjust the pH value to 9-12, then carrying out hydrothermal reaction, and then washing, filtering and drying to obtain carbon spheres;

(2) preparing a precursor: dispersing carbon spheres in absolute ethyl alcohol, and then addingInto FeCl₂And VCl₃Stirring, mixing, standing for 24-48h, washing, filtering, and drying to obtain precursor;

(3) and (3) calcining: the precursor is calcined at high temperature and cooled to obtain FeVO₄The hollow ball.

Preferably, in step (1), 4-20g of glucose is added to 20-80mL of deionized water.

Preferably, in the step (1), the temperature of the hydrothermal reaction is 160-.

Preferably, in the step (1), the drying temperature is 50-80 ℃, and the drying time is 10-24 h.

Preferably, in step (2), 0.1-1g of carbon spheres are dispersed in 20-50ml of absolute ethanol, and then 0.1-0.5mmol of FeCl is added₂And 0.2-1 mmoleVCl₃。

Preferably, in the step (2), the carbon spheres are dispersed in the absolute ethyl alcohol by the following method: adding carbon spheres into absolute ethyl alcohol, performing ultrasonic treatment for 10-30min, and stirring for 30-60 min.

Preferably, in both step (1) and step (2), the washing operation is: washing with deionized water and ethanol for 4-8 times.

Preferably, in the step (2), the drying temperature is 40-60 ℃ and the drying time is 6-12 h.

Preferably, in the step (3), the temperature of the high-temperature calcination is 450-800 ℃, and the holding time is 2-4 hours.

Preferably, the temperature rise rate up to 450-800 ℃ is 1-5 ℃/min.

The invention has the beneficial effects that:

1. the glucose is used as the raw material for preparing the carbon sphere template, so that the method is green, pollution-free, low in price, low in cost and free of toxic and harmful substances.

2. The hydrothermal method is simple to operate, high in yield and easy to produce in large quantities.

3. Can stably generate FeVO with excellent morphology₄。

4. The template is easy to remove and can be removed by only calcining.

5. The method is general, and other metal oxides can also be synthesized into the hollow sphere material by adopting the method.

Drawings

FIG. 1 is a scan of a sample prepared in example 1 of the present invention.

FIG. 2 is an X-ray diffraction pattern of a sample prepared in example 1 of the present invention.

Figure 3 is a scan of a sample prepared in example 2 of the present invention.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples.

In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.

General description of the embodiments

(1) preparing a carbon sphere template: adding 4-20g of glucose into 20-80mL of deionized water, uniformly stirring, adding ammonia water in the stirring process to adjust the pH value to 9-12, carrying out hydrothermal reaction at the temperature of 160 ℃ and 200 ℃ for 5-24h, and washing, filtering and drying to obtain carbon spheres; the drying temperature is 50-80 ℃, and the drying time is 10-24 h.

(2) Preparing a precursor: adding 0.1-1g of carbon spheres into 20-50ml of absolute ethyl alcohol, performing ultrasonic treatment for 10-30min, and then stirring for 30-60 min; then adding 0.1-0.5mmol FeCl₂And 0.2-1mmol VCl₃Stirring, mixing, standing for 24-48h, washing, filtering, and drying to obtain precursor; drying at 40-60 deg.C for 6-12 h;

(3) and (3) calcining: the precursor is subjected to high-temperature calcination at the temperature of 450-800 ℃, the heating rate of 1-5 ℃/min and the heat preservation time of 2-4 hours, and FeVO is obtained after cooling₄The hollow ball.

In the step (1) and the step (2), the washing operation is as follows: washing with deionized water and ethanol for 4-8 times.

Example 1:

dissolving 6 g of glucose in 66 ml of deionized water, stirring uniformly, adding ammonia water to enable the pH value to reach 11, transferring the solution into a 100 ml reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 6 h, cooling, washing with deionized water and ethanol alternately, carrying out suction filtration, and drying at 50 ℃ for 12h to obtain the carbon spheres. Dissolving 0.3 g of carbon spheres in 20 ml of ethanol, performing ultrasonic treatment for 20 min, and stirring for 40min to form ethanol solution of the carbon spheres. 3.33 mmol of FeCl2 and 6.66 mmol of VCl3 were dissolved in a solution of carbon spheres in ethanol. Stirring for 15 h, alternately washing with ethanol and deionized water, filtering, and drying at 50 ℃ for 10h to obtain the precursor. The precursor is placed in a muffle furnace for calcination, and the precursor is heated to 550 ℃ at the heating rate of 1 ℃/min. And preserving the heat for 2 hours, and naturally cooling to room temperature to obtain a final sample. The scanning pattern is shown in figure 1, and the XRD pattern is shown in figure 2.

As can be seen from fig. 1, the sample prepared in example 1 has a distinct spherical morphology. While the hollow structure is visible from the side of the semi-broken ball. From the XRD pattern in FIG. 2, the sample has better crystallinity, and the corresponding is good with standard PDF card PDF #25-0418, which proves that the prepared sample is just FeVO₄。

Example 2:

the calcination temperature of example 1 was changed to 500 ℃ and other conditions were not changed. The scanning picture is shown in figure 3. The hollow sphere structure of the sample is evident from fig. 3, whose surface shell consists of a large number of nanoparticles.

The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims

1. FeVO₄The preparation method of the hollow sphere is characterized by comprising the following steps:

(2) preparing a precursor: dispersing carbon spheres in absolute ethyl alcohol, and thenAdding FeCl₂And VCl₃Stirring, mixing, standing for 24-48h, washing, filtering, and drying to obtain precursor;

2. The method according to claim 1, wherein in the step (1), 4 to 20g of glucose is added to 20 to 80mL of deionized water.

3. The preparation method as claimed in claim 1, wherein the hydrothermal reaction is carried out at a temperature of 160 ℃ to 200 ℃ for 5-24h in step (1).

4. The method according to claim 1, wherein in the step (1), the drying temperature is 50 to 80 ℃ and the drying time is 10 to 24 hours.

5. The method according to claim 1, wherein in the step (2), 0.1 to 1g of carbon spheres are dispersed in 20 to 50ml of anhydrous ethanol, and then 0.1 to 0.5mmol of FeCl is added₂And 0.2-1 mmoleVCl₃。

6. The method according to claim 1, wherein the carbon spheres are dispersed in the absolute ethanol in step (2) by: adding carbon spheres into absolute ethyl alcohol, performing ultrasonic treatment for 10-30min, and stirring for 30-60 min.

7. The method according to claim 1, wherein in both of the step (1) and the step (2), the washing operation is: washing with deionized water and ethanol for 4-8 times.

8. The method according to claim 1, wherein in the step (2), the drying temperature is 40 to 60 ℃ and the drying time is 6 to 12 hours.

9. The method as claimed in claim 1, wherein the temperature of the high-temperature calcination in the step (3) is 450-800 ℃, and the holding time is 2-4 hours.

10. The method as claimed in claim 9, wherein the temperature rise rate of the temperature rise to 450-800 ℃ is 1-5 ℃/min.