CN109326790B

CN109326790B - One-dimensional nano linear sodium titanate and preparation method and application thereof

Info

Publication number: CN109326790B
Application number: CN201811003464.2A
Authority: CN
Inventors: 李建明; 刘合; 金旭; 王晓琦; 焦航; 刘晓丹; 孙亮
Original assignee: Petrochina Co Ltd
Current assignee: Petrochina Co Ltd
Priority date: 2018-08-30
Filing date: 2018-08-30
Publication date: 2021-08-03
Anticipated expiration: 2038-08-30
Also published as: CN109326790A

Abstract

The invention provides one-dimensional nano linear sodium titanate and a preparation method and application thereof. The preparation method of the one-dimensional nano linear sodium titanate comprises the following steps: s1, preparing a peroxide complex dispersion liquid containing titanium; s2, slowly adding a sodium compound into the peroxide complex dispersion liquid containing the titanium to form a solution; s3, adding alcohol into the solution under the conditions of normal temperature and normal pressure to obtain one-dimensional nanometer linear precursor sediment; and S4, precipitating, separating and drying the one-dimensional nano linear precursor, and performing low-temperature heating reaction to obtain a one-dimensional nano linear sodium titanate product. The method has simple process, easily controlled process parameters and easy large-scale industrialization.

Description

One-dimensional nano linear sodium titanate and preparation method and application thereof

Technical Field

The invention relates to the field of materials, in particular to one-dimensional nano linear sodium titanate and a preparation method and application thereof.

Background

Sodium titanate has been widely used in the fields of sodium ion batteries, lithium ion batteries, potassium ion batteries, and the like, and is a hot point for research in the field of materials. The application performance of the sodium titanate material is closely related to the morphological structure of the sodium titanate material. For example, compared with nanoparticles, the one-dimensional nanowire-shaped nanomaterial can reduce grain boundaries among particles, and is beneficial to the transport of carriers in the direction of a long axis. Therefore, compared with the nano particles, the preparation and synthesis of the sodium titanate with the one-dimensional nano linear structure can greatly improve the application effect of the sodium titanate material.

The existing method for synthesizing sodium titanate with a one-dimensional nanometer linear structure mainly adopts hydrothermal reaction, and the method generally adopts nanometer-scale titanium dioxide as a precursor and obtains the sodium titanate through hydrothermal reaction at the temperature of more than 180 ℃ under the condition of 10 mol/L of sodium hydroxide. The hydrothermal process of the preparation method involves high temperature and high pressure, and has high danger; meanwhile, the reaction system is 10 mol/L sodium hydroxide, and has strong corrosivity at a high hydrothermal temperature of more than 180 ℃ and a high hydrothermal pressure of more than 10 atmospheres. The reaction system has very strict requirements on hydrothermal reaction equipment, so that proper reaction equipment is difficult to find, and the synthesis cost is high. In addition, the preparation method uses corrosive alkali with high concentration, which causes difficulty in subsequent separation and purification of sodium titanate products and brings serious pollution to the environment. Therefore, the hydrothermal preparation method of the sodium titanate with the one-dimensional nanometer linear structure still faces a plurality of problems in the aspects of synthesis equipment, synthesis process, subsequent treatment and the like, and the large-scale production cannot be realized.

Therefore, the development of the preparation method which has simple process flow, does not need high-temperature or high-pressure synthesis conditions, is convenient for the large-scale production of the sodium titanate with the one-dimensional nanometer linear structure, and still has significant challenges.

Disclosure of Invention

An object of the present invention is to provide a method for preparing one-dimensional nanowire sodium titanate.

The invention also aims to provide the one-dimensional nano linear sodium titanate prepared by the preparation method.

Another object of the present invention is to provide an electrode material for ion batteries, which is produced from the one-dimensional nanowire-shaped sodium titanate.

The invention also aims to provide a method for preparing titanic acid by using the one-dimensional nano linear sodium titanate as a raw material.

The invention also aims to provide titanic acid prepared by the method.

Another object of the present invention is to provide the use of said titanic acid.

Another object of the present invention is to provide a method for preparing titanium dioxide.

The invention also aims to provide the titanium dioxide prepared by the method.

It is a further object of the present invention to provide the use of said titanium dioxide.

In order to achieve the above object, in one aspect, the present invention provides a method for preparing one-dimensional nanowire-shaped sodium titanate, wherein the method comprises the following steps:

s1, preparing a peroxide complex dispersion liquid containing titanium;

s2, slowly adding a sodium compound into the peroxide complex dispersion liquid containing the titanium to form a solution;

S3, adding alcohol into the solution under the conditions of normal temperature and normal pressure to obtain one-dimensional nanometer linear precursor sediment;

and S4, precipitating, separating and drying the one-dimensional nano linear precursor, and performing low-temperature heating reaction to obtain a one-dimensional nano linear sodium titanate product.

According to some embodiments of the invention, wherein the titanium peroxy complex concentration in the titanium-containing peroxy complex dispersion of step S1 is between 0.01 and 1 mole per liter.

According to some embodiments of the invention, wherein the titanium peroxy complex concentration in the titanium-containing peroxy complex dispersion of step S1 is between 0.05 and 0.5 moles per liter.

According to some embodiments of the invention, the method for preparing the titanium-containing peroxy complex dispersion in step S1 comprises dispersing a titanium source in an aqueous peroxide solution to form a dispersion; the titanium source is selected from one or a combination of more of metallic titanium, titanium ethoxide, titanium isopropoxide, titanium propoxide, tetrabutyl titanate, titanium ethoxide, titanium propoxide, titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, ammonium fluotitanate, titanium nitride, titanium dioxide, metatitanic acid, hydrous titanic acid and orthotitanic acid; the peroxide is selected from one or a combination of hydrogen peroxide, carbamide peroxide and peroxyacetic acid.

According to some embodiments of the present invention, the peroxide complex dispersion containing titanium is prepared in step S1 while a polymer is added to the dispersion; the polymer is selected from one or a combination of several of chitosan, guar gum, methylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyvinyl alcohol, polyacrylamide, polyethylene oxide and polyvinylpyrrolidone; the content of the added polymer in the solution is one ten thousandth to ten percent.

According to some embodiments of the present invention, the content of the polymer added to the solution in step S1 is one thousandth to one hundredth.

According to some embodiments of the present invention, in step S2, the sodium compound is selected from one or more of sodium hydroxide, sodium oxide, sodium peroxide, and sodium superoxide.

According to some embodiments of the invention, the sodium compound is added in step S2 to form a solution having a sodium ion concentration of 0.5 mol/l to 4.0 mol/l.

According to some embodiments of the present invention, the alcohol in step S3 is selected from one or more of methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerol, and polyethylene glycol.

According to some embodiments of the invention, the alcohol is added in an amount of five to fifty percent based on the volume of the solution in step S3.

According to some embodiments of the invention, the alcohol is added in an amount of ten to twenty-five percent based on the volume of the solution in step S3.

According to some embodiments of the present invention, the reaction temperature of the low-temperature heating reaction in step S4 is 150 to 550 ℃; the reaction time of the low-temperature heating reaction is 1 to 24 hours.

According to some embodiments of the present invention, the reaction temperature of the low-temperature heating reaction in step S4 is 150 to 450 ℃.

According to some embodiments of the present invention, the reaction temperature of the low-temperature heating reaction in step S4 is 200 to 450 ℃.

According to some embodiments of the present invention, the reaction time of the low-temperature heating reaction of step S4 is 5 hours to 24 hours.

According to some specific embodiments of the present invention, the method further comprises a step of performing surface modification on the sodium titanate product obtained by the low-temperature heating reaction in step S4, wherein the surface modification comprises loading one or more of the following materials: carbon, carbon nanotubes, graphene, black phosphorus, and metals.

On the other hand, the invention also provides the one-dimensional nano linear sodium titanate prepared by the preparation method.

On the other hand, the invention also provides an electrode material of the ion battery prepared by using the one-dimensional nano linear sodium titanate as a raw material.

According to some specific embodiments of the present invention, the ion battery is selected from a lithium ion battery, a sodium ion battery, a potassium ion battery, or a magnesium ion battery.

On the other hand, the invention also provides a method for preparing titanic acid by using the one-dimensional nano linear sodium titanate as a raw material, wherein the method comprises the step of performing hydrogen ion exchange on the one-dimensional nano linear sodium titanate to obtain a titanic acid product.

According to some embodiments of the invention, the hydrogen ion exchange process comprises: and (3) putting the one-dimensional nano linear sodium titanate into an acid solution for hydrogen ion exchange to obtain the titanic acid.

According to some embodiments of the invention, the acid solution is selected from one or more of nitric acid, hydrochloric acid, sulfuric acid and acetic acid.

According to some embodiments of the invention, wherein the acid solution has a concentration of 0.001 moles per liter to 0.1 moles per liter.

According to some embodiments of the invention, wherein the acid solution has a concentration of 0.01 moles per liter to 0.02 moles per liter.

According to some embodiments of the invention, the hydrogen ion exchange process comprises:

separating and drying the one-dimensional nano linear sodium titanate;

washing and separating the separated and dried one-dimensional nano linear sodium titanate for multiple times;

putting the washed and separated one-dimensional nano linear sodium titanate into an acid solution for hydrogen ion exchange to obtain titanic acid;

washing, separating and drying the obtained titanic acid to obtain a titanic acid product.

In another aspect, the present invention also provides titanic acid prepared by any one of the methods of the present invention.

On the other hand, the invention also provides application of the titanic acid in pollutant adsorption and preparation of ion batteries.

On the other hand, the invention also provides a method for preparing titanium dioxide by using the titanic acid as a raw material, wherein the method comprises the step of carrying out one or a combination of hydrothermal reaction and high-temperature annealing on the titanic acid to obtain a titanium dioxide product.

According to some embodiments of the invention, the hydrothermal reaction is performed at a temperature of 100 to 200 degrees celsius.

According to some embodiments of the invention, the hydrothermal reaction is at a temperature of 150 to 190 degrees celsius.

According to some embodiments of the invention, the hydrothermal reaction is performed at a temperature of 160 ℃ to 180 ℃.

According to some embodiments of the invention, the hydrothermal reaction time is 1 hour to 24 hours.

According to some embodiments of the invention, the hydrothermal reaction time is 12 hours to 24 hours.

According to some embodiments of the invention, the high temperature annealing is at a temperature of 300 to 700 degrees celsius.

According to some embodiments of the invention, the high temperature annealing is at a temperature of 400 to 700 degrees celsius.

According to some embodiments of the invention, the high temperature annealing treatment is performed for 1 hour to 24 hours.

According to some embodiments of the invention, the high temperature annealing treatment is performed for 3 hours to 6 hours.

According to some embodiments of the invention, the method further comprises the step of surface modifying the resulting titanium dioxide product; the surface modification comprises loading one or more of the following materials: carbon, carbon nanotubes, graphene, carbon nitride, black phosphorus, metals, and semiconductors.

On the other hand, the invention also provides titanium dioxide prepared by the method.

In another aspect, the invention also provides applications of the titanium dioxide in the fields of photocatalytic degradation of organic pollutants, photocatalytic decomposition of water for hydrogen production, gas sensing, biomedicine, preparation of catalytic hydrogenation materials, preparation of dye-sensitized solar cells, preparation of perovskite solar cells, preparation of electrode materials of ion cells, or preparation of hydrophilic and hydrophobic materials.

In conclusion, the invention provides sodium titanate and a preparation method and application thereof. The method of the invention has the following advantages:

(1) the method for preparing the sodium titanate, the titanic acid and the titanium dioxide has simple preparation process and easily controlled process parameters, and is easy for large-scale industrial production.

(2) The raw materials are easy to obtain, and the production cost is low.

Drawings

FIG. 1 is a flow chart of the preparation process of the present invention;

FIG. 2 is an SEM image of one-dimensional nanowire-like precursor precipitate products of example 1;

FIG. 3 is an SEM image of one-dimensional nanowire-like sodium titanate product of example 1;

FIG. 4 is a graph of the discharge capacity of the sodium ion battery at different charge and discharge rates when the one-dimensional nanowire-shaped sodium titanate obtained in example 1 is applied to the negative electrode of the sodium ion battery;

FIG. 5 is an SEM image of a titanic acid product of example 10;

FIG. 6 is a graph of the rate of photocatalytic degradation of rhodamine B for anatase phase titanium dioxide obtained in example 13.

Detailed Description

The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.

Example 1

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, 2 g of titanium isopropoxide is dispersed in 50 ml of water under the condition of stirring, 5 ml of hydrogen peroxide with the concentration of 30% is added, and the mixture is stirred to form a titanium-containing peroxy complex suspension. Subsequently, 6 g of sodium hydroxide was added to the above suspension of the peroxy complex, and the mixture was stirred to form a pale yellow transparent solution. Then, 25 ml of ethanol was slowly added to the above transparent solution at room temperature, and after stirring, a one-dimensional nanowire-like precursor precipitate was obtained, whose SEM image is shown in fig. 2. Then, the precursor precipitate is separated and dried,then heating at 250 ℃ for 24 hours to obtain a one-dimensional nano linear sodium titanate product, wherein an SEM picture of the product is shown in figure 3. Fig. 4 is a graph of the discharge capacity of the sodium ion battery at different charge and discharge rates when the one-dimensional nanowire-shaped sodium titanate obtained in this example is applied to the negative electrode of the sodium ion battery. The preparation of the sodium ion battery electrode adopts a blade coating method, and firstly, according to sodium titanate hierarchical structure microspheres: super P: polyvinylidene fluoride (PVDF) is in a mass ratio of 7:2:1, N-methyl pyrrolidone (NMP) is used as a solvent to be mixed into slurry, a blade coater is used for uniformly coating the slurry on a copper foil, then metal lithium is used as a counter electrode in a glove box, and 1mol/L NaClO is adopted as electrolyte ₄Coin cells of type CR2032 were assembled for electrochemical testing, dissolved in EC/DMC (1: 1 by volume) and supplemented with 2% by volume FEC as additive and Glass Fiber as separator. As can be seen from fig. 4, the material has a one-dimensional linear structure due to a small particle size, and the sodium ion battery performance test result of the material is excellent, and the battery still has a very high discharge capacity at a high-rate charge-discharge rate.

Example 2

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, 2 g of titanium isopropoxide is dispersed in 50 ml of water under the condition of stirring, 2 g of urea peroxide is added, and the mixture is stirred to form a titanium-containing peroxy complex suspension. Then, 3 g of sodium hydroxide was added to the above suspension of the peroxy complex, and the mixture was stirred to form a pale yellow transparent solution. Then, 10 ml of isopropanol was slowly added to the above clear solution at room temperature, and a precursor precipitate was obtained after stirring, and its SEM image was substantially identical to that shown in fig. 2. And then, separating and drying the precursor precipitate, and heating at 350 ℃ for 6 hours to obtain a one-dimensional nano linear sodium titanate product, wherein the SEM image of the product is basically consistent with that shown in FIG. 3.

Example 3

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, 2 g of tetrabutyl titanate is dispersed in 50 ml of water under the condition of stirring, 5 ml of hydrogen peroxide with the concentration of 30% is added, and the mixture is stirred to form a peroxide complex suspension containing titanium. Subsequently, 3 g of sodium oxide was added to the above suspension of the peroxy complex, and the mixture was stirred to form a pale yellow transparent solution. Then, 15 ml of methanol was slowly added to the above transparent solution at room temperature, and a precursor precipitate was obtained after stirring, and the SEM image thereof was substantially the same as that shown in fig. 2. And then, separating and drying the precursor precipitate, and heating at the low temperature of 300 ℃ for 8 hours to obtain a one-dimensional nano linear sodium titanate product, wherein the SEM image of the product is basically consistent with that shown in FIG. 3.

Example 4

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, 2 g of titanium sulfate is dissolved in 50 ml of water under the condition of stirring, 5 ml of hydrogen peroxide with the concentration of 30% is added, and the mixture is stirred to form a peroxide complex solution containing titanium. Subsequently, 3 g of sodium peroxide was added to the above peroxy complex solution, and the mixture was stirred to form a pale yellow transparent solution. Then, 20 ml of propanol was slowly added to the above clear solution at room temperature, and a precursor precipitate was obtained after stirring, and the SEM image thereof was substantially identical to that shown in fig. 2. And then, separating and drying the precursor precipitate, and heating at the low temperature of 400 ℃ for 5 hours to obtain a one-dimensional nano linear sodium titanate product, wherein the SEM image of the product is basically consistent with that shown in figure 3.

Example 5

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, 2 g of titanic acid is dispersed in 50 ml of water under the condition of stirring, 4 ml of hydrogen peroxide with the concentration of 30% is added, and the mixture is stirred to form a peroxide complex suspension containing titanium. Subsequently, 2 g of sodium hydroxide was added to the above peroxy complex solution, and the mixture was stirred to form a pale yellow transparent solution. Then, 50 ml of butanol was slowly added to the above clear solution at room temperature, and a precursor precipitate was obtained after stirring, and its SEM image was substantially identical to that shown in fig. 2. And then, separating and drying the precursor precipitate, and heating at the low temperature of 200 ℃ for 24 hours to obtain a one-dimensional nano linear sodium titanate product, wherein the SEM image of the product is basically consistent with that shown in figure 3.

Example 6

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, 2 g of titanyl sulfate is ultrasonically dispersed in 50 ml of water under the stirring condition, 4 ml of hydrogen peroxide with the concentration of 30% is added, and the mixture is stirred to form a peroxide complex solution containing titanium. Subsequently, 8 g of sodium superoxide was added to the above peroxy complex solution, and the mixture was stirred to form a pale yellow transparent solution. Then, 5 ml of ethylene glycol was slowly added to the above transparent solution at room temperature, and a precursor precipitate was obtained after stirring, and the SEM image thereof was substantially the same as that shown in fig. 2. Subsequently, the precursor precipitate was separated and dried, and then heated at a low temperature of 500 ℃ for 2 hours to obtain a one-dimensional nanowire-shaped sodium titanate product, the SEM image of which was substantially the same as that shown in fig. 3.

Example 7

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, 2 g of titanium tetrachloride is dispersed in 50 ml of water by ultrasonic wave under the condition of stirring, then 6 ml of hydrogen peroxide with the concentration of 30% is added, and the mixture is stirred to form a peroxide complex solution containing titanium. Subsequently, 8 g of sodium hydroxide was added to the above peroxy complex solution, and the mixture was stirred to form a pale yellow transparent solution. Then, 5 ml of propylene glycol was slowly added to the above clear solution at room temperature, and a precursor precipitate was obtained after stirring, and the SEM image thereof was substantially the same as that shown in fig. 2. And then, separating and drying the precursor precipitate, and heating at 350 ℃ for 4 hours to obtain a one-dimensional nano linear sodium titanate product, wherein the SEM image of the product is basically consistent with that shown in FIG. 3.

Example 8

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, 2 g of titanium tetrafluoride is ultrasonically dispersed in 50 ml of water under the condition of stirring, then 6 ml of hydrogen peroxide with the concentration of 30 percent and hydroxypropyl methyl cellulose with the concentration of one thousandth are added, and the mixture is stirred to form a peroxo complex solution containing titanium. Subsequently, 8 g of sodium hydroxide was added to the above peroxy complex solution, and the mixture was stirred to form a pale yellow transparent solution. Then, 10 ml of propylene glycol was slowly added to the above clear solution at room temperature, and a precursor precipitate was obtained after stirring, and the SEM image thereof was substantially the same as that shown in fig. 2. And then, separating and drying the precursor precipitate, and heating at the low temperature of 400 ℃ for 3 hours to obtain a one-dimensional nano linear sodium titanate product, wherein the SEM image of the product is basically consistent with that shown in figure 3.

Example 9

According to the flow of preparing one-dimensional nanometer linear sodium titanate shown in figure 1, under the condition of stirring, 2 g of titanium ethoxide is ultrasonically dispersed in 50 ml of water, then 8 ml of hydrogen peroxide with the concentration of 30% and polyvinyl alcohol with the concentration of one percent are added, and the mixture is stirred to form peroxide complex suspension containing titanium. Subsequently, 8 g of sodium hydride was added to the above peroxy complex solution, and the mixture was stirred to form a pale yellow transparent solution. Then, 10 ml of isopropanol was slowly added to the above clear solution at room temperature, and a precursor precipitate was obtained after stirring, and its SEM image was substantially identical to that shown in fig. 2. And then, separating and drying the precursor precipitate, and heating at the low temperature of 400 ℃ for 3 hours to obtain a one-dimensional nano linear sodium titanate product, wherein the SEM image of the product is basically consistent with that shown in figure 3.

Example 10

According to the process for preparing titanic acid shown in fig. 1, the one-dimensional nano linear sodium titanate product obtained in example 1 is washed with deionized water for a plurality of times until the product becomes neutral, and then the product is separated and dispersed in nitric acid solution of 0.01mol/L for hydrogen ion exchange, and then the product is washed with deionized water for a plurality of times until the pH of the washing solution is close to neutral, and then the product is separated and dried, so that titanic acid product is obtained, wherein the SEM picture of the product is shown in fig. 5.

Example 11

According to the flow of preparing titanic acid shown in fig. 1, the one-dimensional nano linear sodium titanate product obtained in example 1 is washed with deionized water for a plurality of times until the product is neutral, and then the product is dispersed in 0.001mol/L hydrochloric acid solution for hydrogen ion exchange, and then the product is washed with deionized water for a plurality of times after the hydrogen ion exchange until the pH of the washing solution is close to neutral, and finally the product is separated and dried to obtain the titanic acid product.

Example 12

According to the process for preparing titanic acid shown in fig. 1, the one-dimensional nano linear sodium titanate product obtained in example 1 is repeatedly washed to neutrality by deionized water, separated and dispersed in 0.1mol/L acetic acid solution for hydrogen ion exchange, repeatedly washed by deionized water after hydrogen ion exchange until the pH of the washing solution is close to neutrality, separated and dried to obtain the titanic acid product.

Example 13

According to the process for preparing titanium dioxide shown in FIG. 1, the one-dimensional nanowire-shaped titanic acid product prepared in example 10 is put into a muffle furnace and annealed at 350 ℃ for 4h to obtain an anatase-phase titanium dioxide product. FIG. 6 is a graph showing the rate of photocatalytic degradation of rhodamine B for anatase phase titanium dioxide obtained in this example. The test condition is that 50mg of the titanium dioxide product prepared in the embodiment is dispersed in 10mg/L rhodamine B solution, and a rate chart of photocatalytic degradation of rhodamine B under the irradiation of a 3-watt LED ultraviolet lamp is adopted; under the same test conditions, P25 was used as a comparative material. As can be seen in FIG. 6, the material has higher performance of photocatalytic decomposition of organic matters than that of the existing commercial P25 product, is about 1.8 times of the rate of the P25 product, and has better application prospect of photocatalytic decomposition of organic pollutants.

Example 14

According to the procedure for preparing titanium dioxide shown in FIG. 1, the titanic acid product obtained in example 10 was placed in a muffle furnace and annealed at 700 ℃ for 1 hour to obtain a rutile phase titanium dioxide product.

Example 15

According to the procedure for preparing titanium dioxide shown in FIG. 1, the titanic acid product prepared in example 10 was put in a muffle furnace and annealed at 300 ℃ for 24 hours to obtain an anatase-phase titanium dioxide product.

Example 16

According to the procedure for preparing titanium dioxide shown in FIG. 1, the titanic acid product prepared in example 10 was dispersed in 100 ml of pure water, and subjected to hydrothermal reaction at 150 ℃ for 12 hours to obtain a titanium dioxide product.

Example 17

According to the procedure for preparing titanium dioxide shown in FIG. 1, the titanic acid product prepared in example 10 was dispersed in 100 ml of pure water, and subjected to hydrothermal reaction at 100 ℃ for 24 hours to obtain a titanium dioxide product.

Example 18

According to the procedure for preparing titanium dioxide shown in FIG. 1, the titanic acid product prepared in example 10 was dispersed in 100 ml of pure water, and subjected to hydrothermal reaction at 200 ℃ for 2 hours to obtain a titanium dioxide product.

Example 19

According to the procedure for preparing titanium dioxide shown in FIG. 1, the titanic acid product prepared in example 10 was dispersed in 100 ml of 0.01mol/L nitric acid solution and subjected to hydrothermal reaction at 160 ℃ for 12 hours to obtain a titanium dioxide product.

Example 20

According to the flow chart of titanium dioxide preparation shown in FIG. 1, the titanic acid product prepared in example 10 is dispersed in 100 ml of pure water, and hydrothermal reaction is carried out for 8h at 120 ℃; and (3) separating and drying the hydrothermal product, putting the hydrothermal product into a muffle furnace, and annealing at 400 ℃ for 2 hours to obtain an anatase phase titanium dioxide product.

Example 21

According to the flow shown in FIG. 1 for preparing titanium dioxide, the titanic acid product prepared in example 10 is put into a muffle furnace and annealed at 300 ℃ for 3 h; dispersing the annealed product in 100 ml of pure water, and carrying out hydrothermal reaction for 15h at 140 ℃ to obtain an anatase phase titanium dioxide product.

Claims

1. A preparation method of one-dimensional nanometer linear sodium titanate comprises the following steps:

s1, preparing a peroxide complex dispersion liquid containing titanium;

2. The process of claim 1 wherein the titanium peroxy complex concentration in the titanium-containing peroxy complex dispersion of step S1 is from 0.01 to 1 mole per liter.

3. The process of claim 2 wherein the titanium peroxy complex concentration in the titanium-containing peroxy complex dispersion of step S1 is from 0.05 to 0.5 moles per liter.

4. The production method according to claim 1, wherein the method for producing the titanium-containing peroxo complex dispersion liquid in step S1 includes dispersing a titanium source in an aqueous peroxide solution to form a dispersion liquid; the titanium source is selected from one or a combination of more of metal titanium, titanium ethoxide, titanium isopropoxide, titanium propoxide, tetrabutyl titanate, titanium ethoxide, titanium propoxide, titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, ammonium fluotitanate, titanium nitride, titanium dioxide, metatitanic acid and titanic acid; the peroxide is selected from one or a combination of hydrogen peroxide, carbamide peroxide and peroxyacetic acid.

5. The production method according to claim 1, wherein the polymer is added to the dispersion while the titanium-containing peroxo complex dispersion is produced in step S1; the polymer is selected from one or a combination of several of chitosan, guar gum, methylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, polyvinyl alcohol, polyacrylamide, polyethylene oxide and polyvinylpyrrolidone; the content of the added polymer in the solution is one ten thousandth to ten percent.

6. The production method according to claim 5, wherein the content of the additive polymer in the solution is one thousandth to one hundredth.

7. The method of claim 1, wherein the sodium compound in step S2 is selected from sodium hydroxide, sodium oxide, sodium peroxide, and sodium superoxide.

8. The production method according to claim 1, wherein the concentration of sodium ions in the solution formed by adding the sodium compound in step S2 is 0.5 mol/l to 4.0 mol/l.

9. The preparation method according to claim 1, wherein the alcohol in step S3 is selected from one or more of methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, glycerol, and polyethylene glycol.

10. The method of claim 1, wherein the alcohol is added in an amount of five to fifty percent based on the volume of the solution in step S3.

11. The method of claim 1, wherein the alcohol is added in an amount of ten to twenty-five percent based on the volume of the solution in step S3.

12. The production method according to claim 1, wherein the reaction temperature of the low-temperature heating reaction of step S4 is 150 to 550 degrees celsius; the reaction time of the low-temperature heating reaction is 1 to 24 hours.

13. The preparation method of claim 12, wherein the temperature of the low-temperature heating reaction of step S4 is 200 to 450 degrees celsius.

14. The preparation method according to any one of claims 1 to 13, further comprising a step of performing surface modification on the one-dimensional nanowire-shaped sodium titanate product obtained by the low-temperature heating reaction in step S4, wherein the surface modification comprises loading one or more of the following materials: carbon, carbon nanotubes, graphene, black phosphorus, and metals.

15. The one-dimensional nanowire-shaped sodium titanate prepared by the preparation method of any one of claims 1 to 14.

16. An electrode material for an ion battery produced from the one-dimensional nanowire-like sodium titanate according to claim 15 as a raw material.

17. The electrode material of claim 16, wherein the ion battery is selected from a lithium ion battery, a sodium ion battery, a potassium ion battery, or a magnesium ion battery.

18. A method for producing titanic acid using the one-dimensional nanowire-shaped sodium titanate of claim 15 as a raw material, wherein the method comprises subjecting the one-dimensional nanowire-shaped sodium titanate to hydrogen ion exchange to obtain a titanic acid product.

19. The method of claim 18, wherein the hydrogen ion exchange process comprises: and (3) putting the one-dimensional nano linear sodium titanate into an acid solution for hydrogen ion exchange to obtain the titanic acid.

20. The method according to claim 19, wherein the acid solution is selected from one or more of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid.

21. The method of claim 19, wherein the acid solution has a concentration of 0.001 moles per liter to 0.1 moles per liter.

22. The method of any one of claims 19 to 21, wherein the hydrogen ion exchange process comprises:

separating and drying the one-dimensional nano linear sodium titanate;

23. A titanic acid prepared by the process of any one of claims 18 to 22.

24. Use of the titanic acid of claim 23 in contaminant adsorption and in the manufacture of an ion battery.

25. Use according to claim 24, wherein the ion battery is selected from a lithium ion battery, a sodium ion battery, a potassium ion battery, or a magnesium ion battery.

26. A method for preparing titanium dioxide from the titanic acid of claim 23, wherein the method comprises subjecting the titanic acid to one or a combination of hydrothermal reaction and high temperature annealing to obtain a titanium dioxide product.

27. The method of claim 26, wherein the temperature of the hydrothermal reaction is from 100 degrees celsius to 200 degrees celsius; the hydrothermal reaction time is 1 hour to 24 hours.

28. The method of claim 26, wherein the high temperature anneal is at a temperature of 300 to 700 degrees celsius; the time of the high-temperature annealing treatment is 1 hour to 24 hours.

29. The method of claim 26, wherein the method further comprises the step of surface modifying the resulting titanium dioxide product; the surface modification comprises loading one or more of the following materials: carbon, carbon nanotubes, graphene, carbon nitride, black phosphorus, metals, and semiconductors.

30. Titanium dioxide produced by the process of any one of claims 26 to 29.

31. The use of the titanium dioxide of claim 30 in the fields of photocatalytic degradation of organic pollutants, photocatalytic decomposition of water to produce hydrogen, gas sensing, biomedicine, preparation of catalytic hydrogenation materials, preparation of dye-sensitized solar cells, preparation of perovskite solar cells, preparation of electrode materials for ion cells, or preparation of hydrophilic and hydrophobic materials.