CN110563036A - bismuth oxide nano material rich in oxygen vacancy and preparation method thereof - Google Patents

bismuth oxide nano material rich in oxygen vacancy and preparation method thereof Download PDF

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CN110563036A
CN110563036A CN201910959328.9A CN201910959328A CN110563036A CN 110563036 A CN110563036 A CN 110563036A CN 201910959328 A CN201910959328 A CN 201910959328A CN 110563036 A CN110563036 A CN 110563036A
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bismuth
bismuth oxide
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oxygen
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张晓东
金森
谢毅
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University of Science and Technology of China USTC
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Abstract

The invention provides a preparation method of an oxygen vacancy-rich bismuth oxide nano material, which comprises the following steps: A) placing metal bismuth in an alcohol solvent of organic amine to carry out heating reaction under a closed condition to obtain layered bismuth; B) and dispersing the layered bismuth into an alcohol aqueous solution, introducing oxygen-containing gas, and reacting to obtain the oxygen vacancy-rich bismuth oxide nano material. The method provided by the invention has low energy consumption, and can synthesize the sheet material with the thickness of nanometer scale under mild conditions. Furthermore, the photoresponse capability of the sample can be effectively improved by introducing oxygen vacancies in the reaction, the reaction capability of the catalyst can be effectively improved by the low-dimensional vacancy structure, the practical value of the material is expanded, and the economic benefit is huge. The preparation method provided by the invention can obtain a large amount of bismuth oxide nanosheets rich in oxygen vacancies with the thickness of 3-10nm at a low temperature, and the obtained powder has the advantages of low cost, high yield and good purity.

Description

Bismuth oxide nano material rich in oxygen vacancy and preparation method thereof
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a bismuth oxide nano material rich in oxygen vacancies and a preparation method thereof.
Background
With the progress and the channel of science and technologythe rapid development of the technology accelerates the use of fossil fuels and simultaneously causes a large amount of carbon dioxide emission, and people realize that photocatalysis has important application prospect in the aspect of solving the problem of carbon dioxide fixation. Compared with the traditional treatment method, the photocatalysis can convert carbon dioxide into a product with commercial value, and has the advantages of low cost, good benefit, high efficiency, no secondary pollution and the like. As a possible alternative to TiO2material of (B), Bi2O3the bandwidth of the photocatalyst is close to 2.84eV, the photocatalyst can be used for photocatalysis under the condition of visible light, and the photocatalyst is an important semiconductor photocatalyst and has wide application prospect.
Due to various special crystal structures of the bismuth oxide, oxygen vacancies are easily generated in the system, and the oxygen vacancies can effectively transfer photo-generated electrons through the surface exciton effect, so that the photo-generated charge separation efficiency can be greatly improved, the response capability of a sample to high-wavelength light is enhanced, the adsorption capability of the sample to carbon dioxide is improved, and the yield can be effectively improved.
Meanwhile, compared with the corresponding bulk material, the two-dimensional crystal with the atomic-level thickness has the advantages that the optical, electrical and biological compatibility and the like are improved, the micro electronic structure and the macro device can be combined together more efficiently, and the performance is better in practical application.
Bismuth oxide is generally synthesized by the following methods: firstly, bismuth is burnt or bismuth metal is put into a high-temperature area saturated with oxygen; directly putting bismuth nitrate powder into a high-temperature area, and firing to obtain bismuth oxide; dissolving bismuth salt in dilute nitric acid solution, adjusting the pH value by using alkaline reagents such as sodium hydroxide and the like until precipitates are settled, washing and drying the precipitates, and treating the precipitates in a high-temperature area to obtain bismuth oxide; fourthly, small particles of metal bismuth and the like are heated and oxidized at 700-900 ℃ by injecting oxygen. The above reactions all require extremely high temperature and have large energy consumption, the maintenance cost of the equipment in practical application is also high, and simultaneously, the reaction is not uniform, so that the appearance of the sample is uncontrollable, the purity of the sample is not high, and the single crystal form bismuth oxide cannot be obtained.
Disclosure of Invention
in view of the above, the technical problem to be solved by the present invention is to provide an oxygen vacancy-rich bismuth oxide nanomaterial and a preparation method thereof, wherein the bismuth oxide nanomaterial can synthesize a sheet material with a thickness of nanometer scale under mild conditions, and has a single shape and high sample purity.
the invention provides a preparation method of an oxygen vacancy-rich bismuth oxide nano material, which comprises the following steps:
A) placing metal bismuth in an alcohol solvent of organic amine to carry out heating reaction under a closed condition to obtain layered bismuth;
B) And dispersing the layered bismuth into an alcohol aqueous solution, introducing gas, and reacting to obtain the bismuth oxide nano material rich in oxygen vacancies.
Preferably, in step a), the organic amine is selected from n-propylamine or n-butylamine;
The alcohol solvent is selected from benzyl alcohol;
the volume ratio of the alcohol solvent to the organic amine is (3-15) to 1.
preferably, the heating reaction temperature is 100-200 ℃, and the heating reaction time is 10-24 hours.
Preferably, the metal bismuth is granular, the metal bismuth is added according to the use amount of an alcohol solvent of organic amine of 15-30 g/L, and the grain size of the metal bismuth is 0.1-50 mu m.
preferably, in step B), the alcohol is selected from one or more of ethylene glycol, methanol, ethanol and isopropanol;
The alcohol is 50% by volume of the aqueous alcohol solution.
Preferably, the content of the layered bismuth in the alcohol aqueous solution is 0.5-10 g/L.
preferably, the gas is a mixed gas of oxygen and argon, air, argon or pure oxygen, and the flow rate of the gas is 1-100L/min.
The invention also provides the bismuth oxide nano material rich in oxygen vacancies, which is prepared by the preparation method and is a nano-sheet layered material.
Preferably, the thickness of the bismuth oxide nano material is 3-10 nm.
compared with the prior art, the invention provides a preparation method of an oxygen vacancy-rich bismuth oxide nano material, which comprises the following steps: A) placing metal bismuth in an alcohol solvent of organic amine to carry out heating reaction under a closed condition to obtain layered bismuth; B) and dispersing the layered bismuth into an alcohol aqueous solution, introducing oxygen-containing gas, and reacting to obtain the oxygen vacancy-rich bismuth oxide nano material. The method provided by the invention consumes much less energy than other preparation methods, and can synthesize the flaky material with the thickness of nanometer scale under mild conditions. Furthermore, the photoresponse capability of the sample can be effectively improved by introducing oxygen vacancies in the reaction, the reaction capability of the catalyst can be effectively improved by the low-dimensional vacancy structure, the practical value of the material is expanded, and the economic benefit is huge. The preparation method provided by the invention can obtain a large amount of bismuth oxide nanosheets rich in oxygen vacancies with the thickness of 3-10nm at a low temperature, and the obtained powder has the advantages of low cost, high yield and good purity.
Drawings
FIG. 1 is a scan of the product obtained in example 1 of the present invention;
FIG. 2 is a transmission diagram of a product obtained in example 2 of the present invention;
FIG. 3 is a transmission diagram of a product obtained in example 3 of the present invention;
FIG. 4 is a transmission diagram of the product obtained in example 4 of the present invention;
FIG. 5 is an XRD (X-ray electron diffraction) analysis chart of a product obtained in example 4 of the present invention;
FIG. 6 is a graph showing an ESR (electron paramagnetic resonance) analysis of a product obtained in example 4 of the present invention;
FIG. 7 is a nuclear magnetic hydrogen spectrum obtained after the product obtained in example 5 of the present invention and a commercially available bismuth oxide block are used for synthesizing dimethyl carbonate;
FIG. 8 is a scanning electron micrograph of a product obtained in example 6 of the present invention;
FIG. 9 is a graph of the X-ray photoelectron spectroscopy oxygen 2p binding energy of the products obtained in examples 1 and 7 of the present invention.
Detailed Description
the invention provides a preparation method of an oxygen vacancy-rich bismuth oxide nano material, which comprises the following steps:
A) placing metal bismuth in an alcohol solvent of organic amine to carry out heating reaction under a closed condition to obtain layered bismuth;
B) And dispersing the layered bismuth into an alcohol aqueous solution, introducing gas, and reacting to obtain the bismuth oxide nano material rich in oxygen vacancies.
firstly, preparing an alcohol solvent of organic amine, wherein the organic amine is selected from n-propylamine or n-butylamine, and preferably n-butylamine;
the alcohol solvent is selected from benzyl alcohol;
The volume ratio of the alcohol solvent to the organic amine is (3-15): 1, preferably (5-12): 1, and more preferably (7-10): 1.
the method comprises the steps of placing metal bismuth in an alcohol solvent of organic amine, and then carrying out heating reaction under a closed condition to obtain layered bismuth.
In the invention, the metal bismuth is granular, the metal bismuth is added according to the use amount of an alcohol solvent of organic amine of 15-30 g/L, and the grain diameter of the metal bismuth is 0.1-50 μm, preferably 0.5-20 μm, and further preferably 1-10 μm.
The sealing conditions are preferably carried out in an autoclave of polytetrafluoroethylene. The temperature of the heating reaction is 100-200 ℃, preferably 120-180 ℃, and the time of the heating reaction is 10-24 hours, preferably 16-20 hours.
And then, washing and drying the heated reaction product to obtain layered bismuth.
And washing by using deionized water until the pH value of the supernatant is 7, and then washing twice by using absolute ethyl alcohol.
the drying temperature is 60-80 ℃, preferably 65-75 ℃, and the drying time is 8-24 hours, preferably 12-20 hours.
preparing an aqueous solution of alcohol, wherein the alcohol is selected from one or more of ethylene glycol, methanol, ethanol and isopropanol, and is preferably isopropanol, ethylene glycol or ethanol;
The alcohol is 50% by volume of the aqueous alcohol solution.
next, the layered bismuth is dispersed in an aqueous alcohol solution to obtain a dispersion liquid. The content of the layered bismuth in the alcohol aqueous solution is 0.5-10 g/L, preferably 1-8 g/L, and more preferably 3-6 g/L.
the method of the dispersion is not particularly limited in the present invention, and ultrasonic dispersion is preferably employed. Wherein the ultrasonic power is 60-120W, and the frequency is 40000-60000 Hz.
and after the dispersion liquid is obtained, introducing gas into the dispersion liquid for reaction to obtain the bismuth oxide nano material rich in oxygen vacancies. The gas is oxygen and argon gas mixed gas, air, argon gas or pure oxygen, and the flow rate of the gas is 1-100L/min, preferably 10-90L/min, and further preferably 30-70L/min. In the present invention, ultrasonic treatment is performed while introducing a gas into the dispersion. The power of ultrasonic treatment is 60-120W, the frequency is 40000-60000 Hz, and the time of ultrasonic treatment is 4-12 hours.
And finally, centrifugally collecting the reaction product, and then washing and drying to obtain the oxygen vacancy-rich bismuth oxide nanosheet powder.
Wherein the rotation speed of the centrifugal collection is 1000-15000 r/min, preferably 5000-10000 r/min; the time is 1 to 20 minutes, preferably 3 to 15 minutes.
The washing is carried out by adopting deionized water to wash until the pH value of the supernatant is 7 and then adopting absolute ethyl alcohol to wash twice.
The drying temperature is 60-80 ℃, preferably 65-75 ℃, and the drying time is 8-24 hours, preferably 12-20 hours.
The invention also provides the bismuth oxide nano material rich in oxygen vacancies, which is prepared by the preparation method and is a nano-sheet layered material. The thickness of the bismuth oxide nano material is 3-10nm, and the color of the bismuth oxide nano material is milky white.
The invention provides a preparation method of bismuth oxide with low energy consumption, high purity, good uniformity and rich oxygen vacancies. The method provided by the invention consumes much less energy than other preparation methods, can synthesize the flaky material with the thickness of nanometer scale under mild conditions, and can effectively improve the reaction capability of the catalyst. Furthermore, by introducing oxygen vacancies in the reaction, the photoresponse capability of the sample can be effectively improved, the practical value of the material is improved, and the method has great economic benefit.
for further understanding of the present invention, the oxygen vacancy rich bismuth oxide nanomaterial provided by the present invention and the preparation method thereof are illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
a preparation method of bismuth oxide rich in oxygen vacancies comprises the following steps:
(1) weighing 25mL of benzyl alcohol, adding 8mL of n-propylamine into the benzyl alcohol, weighing 700mg of metal bismuth, adding the metal bismuth into the benzyl alcohol, and stirring for a moment;
(2) Putting the mixed solution into a polytetrafluoroethylene reaction kettle with the volume of 50mL, sealing, and then putting the reaction kettle into a 180 ℃ oven for 6 hours;
(3) Collecting a product, washing the product by using deionized water until the pH value of supernatant is 7, then washing the product for 2 times by using absolute ethyl alcohol, and drying the product for 12 hours at 80 ℃;
(4) Preparing 100mL of mixed solution of isopropanol and water, wherein the volume ratio is 1: 1;
(5) and (4) adding 300mg of the precursor in the step (3) into the mixed solution in the step (4), and sealing the mixed solution in an open glass bottle. Placing the glass bottle in an ultrasonic cleaner, setting the ultrasonic time to be 6 hours, introducing oxygen into the solution through a glass tube, and setting the flow to be 15L/min;
(6) and taking the upper layer solution, collecting a sample by using a centrifugal machine, wherein the rotating speed of the centrifugal machine is set to 10000r/min, the time is set to 2 minutes, collecting powder, washing the powder by using deionized water until the pH value of the upper layer clear liquid is 7, then washing the powder for 2 times by using absolute ethyl alcohol, drying the powder in a drying box at 80 ℃ for 12 hours, and taking out the powder to obtain the oxygen vacancy-rich bismuth oxide nanosheet powder.
the topography of the dried powder, i.e., a Scanning Electron Microscope (SEM) analysis chart, is shown in fig. 1. Thus, only one shape of the obtained bismuth oxide rich in oxygen vacancies is nano-flake.
Example 2
a preparation method of bismuth oxide rich in oxygen vacancies comprises the following steps:
(1) weighing 30mL of benzyl alcohol, adding 8mL of n-propylamine into the benzyl alcohol, weighing 800mg of metal bismuth, adding the metal bismuth into the benzyl alcohol, and stirring for a moment;
(2) Putting the mixed solution into a polytetrafluoroethylene reaction kettle with the volume of 50mL, sealing, and then putting the reaction kettle into a 180 ℃ oven for 12 hours;
(3) Collecting a product, washing the product by using deionized water until the pH value of supernatant is 7, then washing the product by using absolute ethyl alcohol for 2 times, and drying the product for 12 hours at the temperature of 60 ℃;
(4) preparing 100mL of mixed solution of glycol and water, wherein the volume ratio is 1: 1;
(5) And (4) adding 400mg of the precursor in the step (3) into the mixed solution in the step (4), and sealing the mixed solution in an open glass bottle. Placing the glass bottle in an ultrasonic cleaner, setting the ultrasonic time to be 6 hours, introducing oxygen into the solution through a glass tube, and setting the flow to be 10L/min;
(6) And taking the upper layer solution, collecting a sample by using a centrifugal machine, wherein the rotating speed of the centrifugal machine is set to 10000r/min, the time is set to 2 minutes, collecting powder, washing the powder by using deionized water until the pH value of the upper layer clear liquid is 7, then washing the powder by using absolute ethyl alcohol for 2 times, drying the powder in a drying box at 60 ℃ for 12 hours, and taking out the powder to obtain the oxygen vacancy-rich bismuth oxide nanosheet powder.
the morphology of the powder obtained after drying, i.e. the transmission electron microscopy analysis chart, is shown in fig. 2. Thus, only one shape of the obtained bismuth oxide rich in oxygen vacancies is nano-flake.
Example 3
A preparation method of bismuth oxide rich in oxygen vacancies comprises the following steps:
(1) weighing 30mL of benzyl alcohol, adding 8mL of n-propylamine into the benzyl alcohol, weighing 800mg of metal bismuth, adding the metal bismuth into the benzyl alcohol, and stirring for a moment;
(2) putting the mixed solution into a polytetrafluoroethylene reaction kettle with the volume of 50mL, sealing, and then putting the reaction kettle into a 180 ℃ oven for 12 hours;
(3) collecting a product, washing the product by using deionized water until the pH value of supernatant is 7, then washing the product by using absolute ethyl alcohol for 2 times, and drying the product for 12 hours at the temperature of 60 ℃;
(4) Preparing 100mL of mixed solution of glycol and water, wherein the volume ratio is 1: 1;
(5) And (4) adding 400mg of the precursor in the step (3) into the mixed solution in the step (4), and sealing the mixed solution in an open glass bottle. Placing the glass bottle in an ultrasonic cleaner, setting the ultrasonic time to be 6 hours, introducing argon gas into the solution through a glass tube, and setting the flow to be 10L/min;
(6) and taking the upper layer solution, collecting a sample by using a centrifugal machine, wherein the rotating speed of the centrifugal machine is set to 10000r/min, the time is set to 2 minutes, collecting powder, washing the powder by using deionized water until the pH value of the upper layer clear liquid is 7, then washing the powder by using absolute ethyl alcohol for 2 times, drying the powder in a drying box at 60 ℃ for 12 hours, and taking out the powder to obtain the oxygen vacancy-rich bismuth oxide nanosheet powder.
The morphology of the powder obtained after drying, i.e. the transmission electron microscopy analysis chart, is shown in fig. 3. The obtained bismuth oxide rich in oxygen vacancies is of a nanosheet shape.
Example 4
(1) Weighing 30mL of benzyl alcohol, adding 8mL of n-propylamine into the benzyl alcohol, weighing 800mg of metal bismuth, adding the metal bismuth into the benzyl alcohol, and stirring for a moment;
(2) Putting the mixed solution into a polytetrafluoroethylene reaction kettle with the volume of 50mL, sealing, and then putting the reaction kettle into a 100 ℃ oven for 24 hours;
(3) Collecting a product, washing the product by using deionized water until the pH value of supernatant is 7, then washing the product by using absolute ethyl alcohol for 2 times, and drying the product for 12 hours at the temperature of 60 ℃;
(4) preparing 100mL of mixed solution of ethanol and water, wherein the volume ratio is 1: 1;
(5) And (4) adding 200mg of the precursor in the step (3) into the mixed solution in the step (4), and sealing the mixed solution in an open glass bottle. Placing the glass bottle in an ultrasonic cleaner, setting the ultrasonic time to be 6 hours, introducing mixed gas of oxygen and argon into the solution through a glass tube, wherein the volume ratio is 1:1, and the flow is set to be 10L/min;
(6) And taking the upper layer solution, collecting a sample by using a centrifugal machine, wherein the rotating speed of the centrifugal machine is set to 10000r/min, the time is set to 2 minutes, collecting powder, washing the powder by using deionized water until the pH value of the upper layer clear liquid is 7, then washing the powder by using absolute ethyl alcohol for 2 times, drying the powder in a drying box at 60 ℃ for 12 hours, and taking out the powder to obtain the oxygen vacancy-rich bismuth oxide nanosheet powder.
The morphology of the powder obtained after drying, i.e. the transmission electron microscopy analysis chart, is shown in fig. 4. The obtained bismuth oxide rich in oxygen vacancies is of a nanosheet shape.
The oxygen vacancy-rich bismuth oxide nanosheets obtained in the above examples were subjected to X-ray diffraction (XRD) analysis, and the XRD pattern obtained is shown in fig. 5. By comparing JCPDF standard cards (73-2061) of bismuth oxide, the crystal form of the bismuth oxide nanosheet rich in oxygen vacancies is a tetragonal system, the space group is P4/nmm (129), the diffraction peak intensity is high, the peak type is slightly widened, and the fact that the purity of a sample is high and the appearance is in a nanoscale is obvious.
The oxygen vacancy-rich bismuth oxide nanosheets obtained in the above examples were subjected to electron paramagnetic resonance (ESR) analysis, and the ESR spectrum obtained is shown in fig. 6. As seen from the figure, the prepared sample has obvious test strength change at 2.002 g, which indicates that the sample is rich in oxygen vacancies and has good repeatability.
Example 5
A preparation method of bismuth oxide rich in oxygen vacancies comprises the following steps:
(1) Weighing 30mL of benzyl alcohol, adding 8mL of n-propylamine into the benzyl alcohol, weighing 800mg of metal bismuth, adding the metal bismuth into the benzyl alcohol, and stirring for a moment;
(2) Putting the mixed solution into a polytetrafluoroethylene reaction kettle with the volume of 50mL, sealing, and then putting the reaction kettle into a 180 ℃ oven for 12 hours;
(3) collecting a product, washing the product by using deionized water until the pH value of supernatant is 7, then washing the product by using absolute ethyl alcohol for 2 times, and drying the product for 12 hours at the temperature of 60 ℃;
(4) Preparing 100mL of mixed solution of glycol and water, wherein the volume ratio is 1: 1;
(5) And (4) adding 400mg of the precursor in the step (3) into the mixed solution in the step (4), and sealing the mixed solution in an open glass bottle. Placing the glass bottle in an ultrasonic cleaner, setting the ultrasonic time to be 6 hours, introducing argon gas into the solution through a glass tube, and setting the flow to be 10L/min;
(6) and taking the upper layer solution, collecting a sample by using a centrifugal machine, wherein the rotating speed of the centrifugal machine is set to 10000r/min, the time is set to 2 minutes, collecting powder, washing the powder by using deionized water until the pH value of the upper layer clear liquid is 7, then washing the powder by using absolute ethyl alcohol for 2 times, drying the powder in a drying box at 60 ℃ for 12 hours, and taking out the powder to obtain the oxygen vacancy-rich bismuth oxide nanosheet powder.
the dried powder and the commercial bulk bismuth oxide are respectively used for catalyzing carbon dioxide marked by the isotope carbon 13 and methanol to generate dimethyl carbonate, and the nuclear magnetic hydrogen spectrum of the obtained result is shown in figure 7.
Example 6
a preparation method of bismuth oxide rich in oxygen vacancies comprises the following steps:
(1) Weighing 25mL of benzyl alcohol, adding 8mL of n-butylamine into the benzyl alcohol, weighing 700mg of metal bismuth, adding the bismuth into the benzyl alcohol, and stirring for a moment;
(2) putting the mixed solution into a polytetrafluoroethylene reaction kettle with the volume of 50mL, sealing, and then putting the reaction kettle into a 180 ℃ oven for 6 hours;
(3) collecting a product, washing the product by using deionized water until the pH value of supernatant is 7, then washing the product for 2 times by using absolute ethyl alcohol, and drying the product for 12 hours at 80 ℃;
(4) preparing 100mL of mixed solution of isopropanol and water, wherein the volume ratio is 1: 1;
(5) And (4) adding 300mg of the precursor in the step (3) into the mixed solution in the step (4), and sealing the mixed solution in an open glass bottle. Placing the glass bottle in an ultrasonic cleaner, setting the ultrasonic time to be 6 hours, introducing oxygen into the solution through a glass tube, and setting the flow to be 15L/min;
(6) And taking the upper layer solution, collecting a sample by using a centrifugal machine, wherein the rotating speed of the centrifugal machine is set to 10000r/min, the time is set to 2 minutes, collecting powder, washing the powder by using deionized water until the pH value of the upper layer clear liquid is 7, then washing the powder for 2 times by using absolute ethyl alcohol, drying the powder in a drying box at 80 ℃ for 12 hours, and taking out the powder to obtain the oxygen vacancy-rich bismuth oxide nanosheet powder.
the topography of the dried powder, i.e., a Scanning Electron Microscope (SEM) analysis chart, is shown in fig. 8. Thus, only one shape of the obtained bismuth oxide rich in oxygen vacancies is nano-flake. Also, the product obtained in this example is significantly thinner than the product obtained in example 1.
Example 7
A preparation method of bismuth oxide rich in oxygen vacancies comprises the following steps:
(1) weighing 25mL of benzyl alcohol, adding 8mL of n-propylamine into the benzyl alcohol, weighing 700mg of metal bismuth, adding the metal bismuth into the benzyl alcohol, and stirring for a moment;
(2) putting the mixed solution into a polytetrafluoroethylene reaction kettle with the volume of 50mL, sealing, and then putting the reaction kettle into a 180 ℃ oven for 6 hours;
(3) collecting a product, washing the product by using deionized water until the pH value of supernatant is 7, then washing the product for 2 times by using absolute ethyl alcohol, and drying the product for 12 hours at 80 ℃;
(4) preparing 100mL of mixed solution of isopropanol and water, wherein the volume ratio is 1: 1;
(5) And (4) adding 300mg of the precursor in the step (3) into the mixed solution in the step (4), and sealing the mixed solution in an open glass bottle. Placing the glass bottle in an ultrasonic cleaner, setting the ultrasonic time to be 6 hours, introducing argon gas into the solution through a glass tube, and setting the flow to be 15L/min;
(6) And taking the upper layer solution, collecting a sample by using a centrifugal machine, wherein the rotating speed of the centrifugal machine is set to 10000r/min, the time is set to 2 minutes, collecting powder, washing the powder by using deionized water until the pH value of the upper layer clear liquid is 7, then washing the powder for 2 times by using absolute ethyl alcohol, drying the powder in a drying box at 80 ℃ for 12 hours, and taking out the powder to obtain the oxygen vacancy-rich bismuth oxide nanosheet powder.
The powder obtained after drying had an X-ray photoelectron spectroscopy oxygen 2p binding energy chart as shown in FIG. 9. As can be seen from fig. 9, the graph of the ultrasonic wave under argon gas is the graph of the oxygen 2p binding energy of the X-ray photoelectron spectrum of the product prepared in this example, and the graph of the ultrasonic wave under oxygen gas is the graph of the oxygen 2p binding energy of the X-ray photoelectron spectrum of the product prepared in example 1. As can be seen from fig. 9, the amount of oxygen vacancies of the nanoplatelets generated under argon is greater than that generated under oxygen.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. the preparation method of the bismuth oxide nano material rich in oxygen vacancies is characterized by comprising the following steps:
A) Placing metal bismuth in an alcohol solvent of organic amine to carry out heating reaction under a closed condition to obtain layered bismuth;
B) And dispersing the layered bismuth into an alcohol aqueous solution, introducing gas, and reacting to obtain the bismuth oxide nano material rich in oxygen vacancies.
2. the process according to claim 1, wherein in step a), the organic amine is selected from n-propylamine or n-butylamine;
the alcohol solvent is selected from benzyl alcohol;
the volume ratio of the alcohol solvent to the organic amine is (3-15) to 1.
3. the method according to claim 1, wherein the temperature of the heating reaction is 100 to 200 ℃ and the time of the heating reaction is 10 to 24 hours.
4. the preparation method according to claim 1, wherein the metal bismuth is in a granular form, and is added in an amount of 15-30 g/L of an alcohol solvent of organic amine, and the grain size of the metal bismuth is 0.1-50 μm.
5. The method according to claim 1, wherein in step B), the alcohol is selected from one or more of ethylene glycol, methanol, ethanol and isopropanol;
the alcohol is 50% by volume of the aqueous alcohol solution.
6. The preparation method according to claim 1, wherein the content of the layered bismuth in the aqueous alcohol solution is 0.5-10 g/L.
7. the method according to claim 1, wherein the gas is a mixture of oxygen and argon, air, argon or pure oxygen, and the flow rate of the gas is 1-100L/min.
8. the bismuth oxide nanomaterial rich in oxygen vacancies prepared by the preparation method according to any one of claims 1 to 7, wherein the bismuth oxide nanomaterial is a nanosheet layered material.
9. The bismuth oxide nanomaterial according to claim 8, wherein the thickness of the bismuth oxide nanomaterial is 3-10 nm.
CN201910959328.9A 2019-10-10 2019-10-10 bismuth oxide nano material rich in oxygen vacancy and preparation method thereof Pending CN110563036A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113731396A (en) * 2021-09-13 2021-12-03 江西科技师范大学 Oxygen-enriched defect Bi2O4Photocatalytic material, preparation method and application thereof
CN114011398A (en) * 2021-11-19 2022-02-08 辽宁大学 3D flower-like Zn3In2S6@Bi2O4/β-Bi2O3double-Z-type heterojunction photocatalyst and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113731396A (en) * 2021-09-13 2021-12-03 江西科技师范大学 Oxygen-enriched defect Bi2O4Photocatalytic material, preparation method and application thereof
CN113731396B (en) * 2021-09-13 2023-04-11 江西科技师范大学 Oxygen-enriched defect Bi 2 O 4 Photocatalytic material, preparation method and application thereof
CN114011398A (en) * 2021-11-19 2022-02-08 辽宁大学 3D flower-like Zn3In2S6@Bi2O4/β-Bi2O3double-Z-type heterojunction photocatalyst and application thereof
CN114011398B (en) * 2021-11-19 2023-01-17 辽宁大学 3D flower-like Zn 3 In 2 S 6 @Bi 2 O 4 /β-Bi 2 O 3 double-Z-type heterojunction photocatalyst and application thereof

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