CN114229892A

CN114229892A - Ion implantation doped bismuth oxide and preparation method and application thereof

Info

Publication number: CN114229892A
Application number: CN202111590671.4A
Authority: CN
Inventors: 赵科湘; 谢宗华
Original assignee: Zhuzhou Keneng New Material Co ltd
Current assignee: Zhuzhou Keneng New Material Co ltd
Priority date: 2021-12-23
Filing date: 2021-12-23
Publication date: 2022-03-25
Anticipated expiration: 2041-12-23
Also published as: CN114229892B

Abstract

The invention discloses ion implantation doped bismuth oxide and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing bismuth nitrate and citric acid to obtain a mixture, adding the mixture into water to obtain slurry, heating the slurry in water bath to obtain sol, evaporating water from the sol to obtain gel, calcining the gel to obtain nano bismuth oxide particles, pressing and molding the nano bismuth oxide particles to obtain bismuth oxide green sheets, and sintering the bismuth oxide green sheets to obtain bismuth oxideThe slice is prepared by placing bismuth oxide slice on the substrate of ion implanter, implanting doping ions into bismuth oxide slice to obtain doped bismuth oxide, and doping Na into bismuth oxide by the above method⁺Can obviously improve the hydrophilic performance of bismuth oxide, greatly improve the application of the bismuth oxide in glass coloring, and the invention is more pioneering to use non-metallic ion Si⁴⁺Doping with bismuth oxide and doping with Si⁴⁺Can greatly improve the performances of catalyzing and degrading organic wastewater, high-temperature superconductivity and the like.

Description

Ion implantation doped bismuth oxide and preparation method and application thereof

Technical Field

The invention relates to a doped powder material, in particular to ion implantation doped bismuth oxide and a preparation method and application thereof.

Background

Bismuth oxide is also called bismuth trioxide, is one of the most important compounds of bismuth, has alpha, beta, gamma and delta crystal forms, is widely applied, not only can be used as an organic synthesis catalyst, a ceramic colorant and a glass additive, but also can be used for manufacturing nuclear engineering glass and nuclear reactor fuel, and can be used for special occasions such as semiconductor electronic materials, special functional ceramic materials, cathode ray tube inner wall coatings and the like; the particle size and uniformity of bismuth oxide have great influence on the use of the catalytic performance and the like, the bismuth oxide is an important doped powder material in the electronic industry, ion doping is mainly used for surface modification of semiconductor materials and comprises metal ion doping and non-metal ion doping, and the bismuth oxide doped with different metals has obvious changes in the aspects of photoelectric characteristics and the like, such as Cu doping²⁺、Fe³⁺、Co²⁺The matching of the absorption spectrum of the plasma bismuth oxide with sunlight is obviously improved, and the photocatalytic performance of the plasma bismuth oxide is more favorably improved.

Currently, methods for ion doping bismuth oxide include a coprecipitation method in which bismuth is doped with Bi, an impregnation method, a sol-gel method, and the like³⁺And the solution doped with ions is slowly added into the solution containing excessive precipitator, and is stirred to obtain more uniform precipitate, and the precipitate is subjected to heat treatment to obtain the required material; the impregnation method is to prepare the required bismuth oxide by impregnating bismuth oxide in a salt solution containing metal ions, and the sol-gel method is to add metal ion inorganic salt into bismuth oxide sol and then obtain the final ion-doped bismuth oxide through subsequent treatment; these methods all have major defects, such as uneven ion doping distribution and incapability of controlling crystal form and particle size of bismuth oxide, which ultimately affect the use effect of the finished product, and the method can not dope bismuth oxide with C⁺、Si⁴⁺Plasma non-metal ions; and the dopant ion concentration cannot be precisely controlled.

Disclosure of Invention

In view of the problems in the prior art, the invention aims to provide ion implantation doped bismuth oxide and a preparation method and application thereof. The invention adopts an ion implantation methodThe nano bismuth oxide film is doped with metal ions Na⁺And non-metal ion Si⁴⁺Thereby obviously improving the photocatalytic performance and the electrical conductivity of the bismuth oxide and improving the performances of the bismuth oxide in the aspects of glass coloring, catalytic degradation of organic wastewater, high-temperature superconductivity and the like. The method of the invention has low power consumption, material saving, no toxicity and by-products and environmental protection.

In order to achieve the purpose, the technical solution of the invention is as follows:

the invention relates to a preparation method of ion implantation doped bismuth oxide, which comprises the following steps: mixing bismuth nitrate and citric acid to obtain a mixture, adding the mixture into water to obtain slurry, heating the slurry in a water bath to obtain sol, evaporating water from the sol to obtain gel, calcining the gel to obtain nano bismuth oxide particles, pressing and molding the nano bismuth oxide particles to obtain bismuth oxide green sheets, sintering the bismuth oxide green sheets to obtain bismuth oxide sheets, placing the bismuth oxide sheets on a substrate of an ion implanter, and injecting doping ions into the bismuth oxide sheets to obtain the doped bismuth oxide.

In a preferred embodiment, the ratio of the amounts of the bismuth nitrate and the citric acid is 1: 1-1.5.

In a preferred scheme, the solid-liquid mass volume ratio of the mixture to water is 59.5 g: 100-.

In a preferable scheme, the water bath heating temperature is 90-95 ℃, and the water bath heating time is 3-5 h.

Preferably, the gel is calcined at 350-450 ℃ for 1-2h to obtain the nano bismuth oxide particles.

In a preferable scheme, the particle size of the nano bismuth oxide particles is 50nm-1.5 μm.

Preferably, the pressure of the compression molding is 2-4 MPa.

The inventor finds that the more uniform the bismuth oxide sheet is, the higher the uniformity of the doped ions after final ion implantation is, so that the material performance is better, and the bismuth oxide green sheet can be very flat and uniform by calcining the gel at 350-450 ℃ to obtain nano bismuth oxide particles, and then pressing and forming the nano bismuth oxide particles, so that the bismuth oxide green sheet can be finally calcined to obtain the bismuth oxide sheet with excellent uniformity.

However, the pressure of the compression molding needs to be effectively controlled during the compression process, and the uniform and complete bismuth oxide flakes can be obtained only within the scope of the invention.

Preferably, the sintering temperature is 700-750 ℃, and the sintering time is 30-60 min.

Preferably, the bismuth oxide flake has a plane size of 12X 12-20X 20mm and a thickness of 1-1.2 mm.

Preferably, the temperature of the substrate is controlled to be 750-800 ℃ and the ion acceleration voltage is controlled to be 30-60KeV when the doping ions are implanted.

The inventors have found that by controlling the substrate temperature, and thus the acceleration voltage, within the above ranges, the distribution of the final doping ions in the bismuth oxide is the most uniform, and the resulting doped bismuth oxide has the best performance.

Preferably, the implantation amount of the doping ions is 50-200 ppm.

The inventors have found that controlling the amount of doped ions implanted in the above range optimizes the performance of the finally obtained doped bismuth oxide.

In a preferred embodiment, the dopant ion is Na⁺Or Si⁴⁺。

The inventors found that doping bismuth oxide with Na⁺Can obviously improve the hydrophilic performance of bismuth oxide, greatly improve the application of the bismuth oxide in glass coloring, and the invention is more pioneering to use non-metallic ion Si⁴⁺Doping with bismuth oxide and doping with Si⁴⁺Can greatly improve the performances of catalyzing and degrading organic wastewater, high-temperature superconductivity and the like.

The invention also provides the doped bismuth oxide prepared by the preparation method.

The invention also provides application of the doped bismuth oxide prepared by the preparation method.

Preferably, when the doping ion in the doped bismuth oxide is Na⁺In time, doped bismuth oxide was applied to the glass for coloration.

Preferably, when the doping ion in the doped bismuth oxide is Si⁴⁺When the bismuth oxide is used, the doped bismuth oxide is applied to catalytic degradation of organic wastewater.

Advantageous effects

The invention discloses a method for doping metal ions Na in a nano bismuth oxide thin block by an ion implantation method⁺And non-metal ion Si⁴⁺The inventors found that Na was doped in bismuth oxide⁺Can obviously improve the hydrophilic performance of bismuth oxide, greatly improve the application of the bismuth oxide in glass coloring, and the invention is more pioneering to use non-metallic ion Si⁴⁺Doping with bismuth oxide and doping with Si⁴⁺Can greatly improve the performances of catalyzing and degrading organic wastewater, high-temperature superconductivity and the like. Thereby widening the performance of the bismuth oxide in the application aspects of glass coloring, catalytic degradation of organic wastewater, high-temperature superconduction and the like.

Detailed Description

An ion implantation bismuth oxide doping method is characterized in that metal ions and non-metal ions are doped into bismuth oxide through an ion implantation method.

Example 1

Preparing 20g of citric acid and 39.5g of bismuth nitrate, uniformly mixing, adding the mixture into a 500ml beaker, adding 100ml of ultrapure water, heating the mixture in a water bath at 90 ℃ for 5 hours to generate sol, evaporating the water to obtain gel, calcining the gel at 400 ℃ for 1 hour to obtain nano bismuth oxide particles, pressing the nano bismuth oxide into 12 x 1mmb thin blocks under the condition of 2MPa, putting the bismuth oxide into an ion implanter, adjusting the substrate temperature to 780 ℃, adjusting the ion acceleration voltage to 50KeV, and injecting Na into the bismuth oxide⁺And the concentration is 100ppm, the obtained sodium ion-doped bismuth oxide is re-powdered and is compared with pure bismuth oxide in a hydrophilicity test, and the obtained results are shown in table 1:

TABLE 1 hydrophilicity before and after bismuth oxide doping

Material	Contact angle
		Bi₂O₃	＞90°
Doping with Na⁺Bi₂O₃	0°

The hydrophilicity of the bismuth oxide doped with sodium ions is obviously improved.

Comparative example 1

The other conditions were the same as in example 1 except that the substrate temperature was 830 ℃, and as a result, the resulting sodium ion-doped bismuth oxide was reduced in uniformity and lower in hydrophilicity than in example 1 (table 2).

Table 2 bismuth oxide doped hydrophilicity in example 1 and comparative example 1

Example 2

Preparing 20g of citric acid and 39.5g of bismuth nitrate, uniformly mixing, adding the mixture into a 500ml beaker, adding 100ml of ultrapure water, heating the mixture in a water bath at 90 ℃ for 5 hours to generate sol, evaporating the water to obtain gel, calcining the gel at 400 ℃ for 1 hour to obtain nano bismuth oxide particles, pressing the nano bismuth oxide into 12 x 1mmb thin blocks under the condition of 2MPa, putting the bismuth oxide into an ion implanter, adjusting the substrate temperature to 780 ℃, adjusting the ion acceleration voltage to 50KeV, and injecting Si into the bismuth oxide⁴⁺And the concentration is 150ppm, the obtained silicon ion-doped bismuth oxide is prepared into powder again and is subjected to a rhodamine B photocatalytic degradation test with pure bismuth oxide, and the obtained results are shown in Table 3

Table 3 catalytic degradation test before and after doping of bismuth oxide.

Material	Time (min)	Degradation Rate (%)
			Bi₂O₃	120	55
Doping of Si⁴⁺Bi₂O₃	120	100

Comparative example 2

The other conditions were the same as in example 2 except that the substrate temperature was 830 ℃, and as a result, the uniformity of the obtained sodium ion-doped bismuth oxide was reduced and the degradation efficiency was lower than that of example 2 (table 4).

Table 4 photocatalytic degradation rates of bismuth oxide doping in example 2 and comparative example 2

For the convenience of the reader, the above description has focused on a representative sample of all possible embodiments, a sample that is illustrative of the principles of the invention, and the best mode contemplated for carrying out the invention. The description is not intended to be exhaustive of all possible variations. Other variations or modifications not described are possible.

Claims

1. A preparation method of ion implantation doped bismuth oxide is characterized by comprising the following steps: the method comprises the following steps: mixing bismuth nitrate and citric acid to obtain a mixture, adding the mixture into water to obtain slurry, heating the slurry in a water bath to obtain sol, evaporating water from the sol to obtain gel, calcining the gel to obtain nano bismuth oxide particles, pressing and molding the nano bismuth oxide particles to obtain bismuth oxide green sheets, sintering the bismuth oxide green sheets to obtain bismuth oxide sheets, placing the bismuth oxide sheets on a substrate of an ion implanter, and injecting doping ions into the bismuth oxide sheets to obtain the doped bismuth oxide.

2. The method according to claim 1, wherein the ion implantation doping bismuth oxide is prepared by: the mass ratio of the bismuth nitrate to the citric acid is 1: 1-1.5;

the solid-liquid mass-volume ratio of the mixture to water is 59.5 g: 100-.

3. The method according to claim 1, wherein the ion implantation doping bismuth oxide is prepared by: the temperature of the water bath heating is 90-95 ℃, and the time of the water bath heating is 3-5 h.

4. The method according to claim 1, wherein the ion implantation doping bismuth oxide is prepared by: calcining the gel at the temperature of 350-450 ℃ for 1-2h to obtain nano bismuth oxide particles;

the particle size of the nano bismuth oxide particles is 50nm-1.5 mu m.

5. The method according to claim 1, wherein the ion implantation doping bismuth oxide is prepared by: the pressure of the compression molding is 2-4 MPa.

6. The method according to claim 1, wherein the ion implantation doping bismuth oxide is prepared by: the sintering temperature is 700-750 ℃, and the sintering time is 30-60 min;

the plane size of the bismuth oxide sheet is 12 x 12-20 x 20mm, and the thickness is 1-1.2 mm.

7. The method according to claim 1, wherein the ion implantation doping bismuth oxide is prepared by: when the doped ions are injected, the temperature of the substrate is controlled to be 750-800 ℃, and the ion acceleration voltage is controlled to be 30-60 KeV.

8. The method according to claim 1, wherein the ion implantation doping bismuth oxide is prepared by: the implantation amount of the doping ions is 50-200 ppm; the doped ion is Na⁺Or Si⁴⁺。

9. Doped bismuth oxide prepared by the process according to any one of claims 1 to 8.

10. Use of a doped bismuth oxide prepared by the preparation method according to any one of claims 1 to 8, characterized in that: when the doping ion in the doped bismuth oxide is Na⁺When in use, the doped bismuth oxide is applied to glass coloring;

when the doping ion in the doped bismuth oxide is Si⁴⁺When the bismuth oxide is used, the doped bismuth oxide is applied to catalytic degradation of organic wastewater.