CN113083335A - Preparation method and application of bismuth tungstate-lanthanum phosphate heterojunction material - Google Patents

Preparation method and application of bismuth tungstate-lanthanum phosphate heterojunction material Download PDF

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CN113083335A
CN113083335A CN202110306111.5A CN202110306111A CN113083335A CN 113083335 A CN113083335 A CN 113083335A CN 202110306111 A CN202110306111 A CN 202110306111A CN 113083335 A CN113083335 A CN 113083335A
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韩布兴
翟建新
吴海虹
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East China Normal University
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Abstract

The invention discloses a preparation method and application of bismuth tungstate-lanthanum phosphate heterojunction material, which is characterized in that bismuth tungstate is grown on the basis of lanthanum phosphate to form Bi with a general formula2WO6@LaPO4-x of a powdered heterojunction material; adding Bi2WO6@LaPO4Under the illumination of light, carbon dioxide is used as a gas atmosphere, acetonitrile and water are used as solvents, and alkyl tertiary amine is used as a reactant, so that the corresponding olefin can be efficiently generated by photocatalysis of the alkyl tertiary amine. Compared with the prior art, the invention has the advantages of high catalytic activity, simple preparation, easily obtained raw materials and productionThe method has low cost, high yield, environmental protection and wide application prospect when being used for preparing corresponding olefin by photocatalysis of alkyl tertiary amine.

Description

Preparation method and application of bismuth tungstate-lanthanum phosphate heterojunction material
Technical Field
The invention relates to the technical field of photochemistry, in particular to a preparation method of a bismuth tungstate-lanthanum phosphate heterojunction material and application of the bismuth tungstate-lanthanum phosphate heterojunction material in preparation of olefin by photocatalysis of alkyl tertiary amine.
Background
Tertiary amines are functional compounds that are ubiquitous in nature and can also serve as a source of nitrogen in many pharmaceuticals, materials, and industrial chemicals. Therefore, organic fragments generated by cleavage of C-N bonds in organic synthesis have attracted a great deal of attention from chemists. Due to the excessive consumption of fossil fuels, artificial carbon emission is becoming a basic challenge facing us in this century, and how to develop a new energy preparation method is meaningful. Olefins, as an important chemical raw material, are not only present in natural products, drug molecules and polymeric materials, but also are important synthetic intermediates in organic reactions, where further conversion can occur.
Olefin synthesis is a large number of processes, of which the synthesis of olefins by C-N cleavage in amines remains one of the classical and very important processes. Common reactions include Cope elimination and Hofmann elimination, but the common reactions have certain limitations, require harsh reaction conditions such as high temperature and high pressure, and use organic reagents with high toxicity and are easy to pollute the environment. Therefore, there is a need to develop a non-toxic green olefin production process.
Photocatalysis has obvious advantages of simplicity and economy due to the utilization of solar energy, an inexhaustible energy source. Since 1979 by TiO2Since the pioneering work on this basis, many photocatalytic systems derived from metal oxides, metal sulfides, and metal nitrides have been widely developed. A heterojunction structure composed of two semiconductors has a great advantage in photoelectron transfer behavior compared to a single semiconductor. Among various semiconductors, Bi2WO6It has been extensively studied due to its narrow bandgap (2.58eV), high stability and low cost. However, Bi2WO6The photocatalytic performance of (a) is significantly limited by the rapid recombination rate of electron-hole pairs. And lanthanum phosphate (LaPO)4) A conduction band with longer carrier lifetime and stronger reduction capability, but a forbidden bandIs wide and difficult to be excited by visible light, so that the research progress of the method is limited. Therefore, it is necessary to develop a new catalyst capable of utilizing the combination strategy of two semiconductors to form a heterojunction to take advantage of the advantages of the two semiconductors, and develop a suitable semiconductor composite photocatalyst for photocatalytic alkyl tertiary amine to prepare olefin.
Disclosure of Invention
The invention aims to provide a preparation method and application of a bismuth tungstate-lanthanum phosphate heterojunction material aiming at the defects of the prior art, and the bismuth tungstate is grown on the basis of lanthanum phosphate to form a general formula of Bi2WO6@LaPO4-x of a powdery heterojunction material of Bi2WO6@LaPO4The-x is a catalyst, acetonitrile and water are used as solvents in the atmosphere of illumination and carbon dioxide, the synthetic reaction of preparing olefin from alkyl tertiary amine is efficiently photo-catalyzed, the yield is high, the catalyst is simple to prepare, raw materials are easy to obtain, the production cost is low, the catalytic activity is high, and the method is green and environment-friendly and has wide application prospect.
The purpose of the invention is realized as follows: a process for preparing bismuth tungstate-lanthanum phosphate heterojunction material is characterized in that lanthanum phosphate and bismuth tungstate are adopted to synthesize Bi with a general formula2WO6@LaPO4-x, the specific preparation of which comprises the following steps:
a, step a: preparation of lanthanum phosphate
Will be (NH)4)2HPO4And La (NO)3)3·6H2O and deionized water in a ratio of 1 mmol: 1-3 mmol: mixing 10-30 mL of the components according to a molar volume ratio, stirring the mixture to form uniform colloid, keeping the temperature at 25 ℃ for 1-24 hours, naturally cooling the mixture to room temperature after reaction, washing the precipitate with distilled water, and drying the precipitate at 50-80 ℃ for 10-24 hours to obtain a product LaPO4And (4) nanorod powder.
b, step (b): preparation of solution A
LaPO prepared by the method4Nanorod powder and Bi (NO)3)3·5H2O and deionized water were mixed at a ratio of 1 g: 2.5-20 mmol: 10-30 mL of the solution A is mixed.
c, step (c): preparation of solution B
Cetyl trimethyl ammonium bromide and Na2WO4·2H2O and deionized water 0.025 g: 2.5-20 mmol: 10-30 mL of the mixture is mixed to form a solution B.
d, step: preparation of heterojunction materials
Dropwise adding the prepared solution A into the solution B, stirring and mixing, keeping the temperature at 120-180 ℃ for 12-24 hours, naturally cooling to room temperature after reaction, washing the precipitate with distilled water, and drying at 50-80 ℃ for 10-24 hours to obtain a powdery product, namely a bismuth tungstate-lanthanum phosphate heterojunction material with a general formula of Bi2WO6@LaPO4-x 。
The application of bismuth tungstate-lanthanum phosphate heterojunction material is characterized in that Bi is used2WO6@LaPO4-x is a catalyst, carbon dioxide is used as a gas atmosphere, acetonitrile and water are used as solvents to carry out photocatalytic reaction of alkyl tertiary amine for preparing olefin, and the molar volume ratio of the catalyst to the alkyl tertiary amine, the acetonitrile and the water is as follows: 1 mmol: 0.1-100 mmol: 0.1-100 mmol: 0.1-100 mL; the alkyl tertiary amine is triethylamine, tripropylamine, diisopropylethylamine or other alkyl tertiary amine; the photocatalytic reaction time is 1-24 hours.
Compared with the prior art, the invention has the following remarkable technical effects and advantages:
1) bismuth tungstate grows in situ on the basis of lanthanum phosphate to obtain bismuth tungstate with a general formula of Bi2WO6@LaPO4The powder catalyst of-x has simple method and wide application prospect.
2) Using the Bi2WO6@LaPO4-x of a powdered catalyst. Can efficiently catalyze the alkyl tertiary amine to generate corresponding olefin, and provides a novel green method for preparing the olefin.
Drawings
FIG. 1 is a scanning electron microscope image of the product prepared in example 3;
FIG. 2 is a transmission electron microscope image of the product prepared in example 3;
FIG. 3 is an X-ray diffraction image of the product prepared in example 3;
FIG. 4 is an X-ray photoelectron spectroscopy image of the product prepared in example 3;
FIG. 5 is a Raman spectrum image of the product prepared in example 3;
FIG. 6 is a graph showing the activity of photocatalytic alkyl tertiary amines of examples 6 to 8 in olefin production;
FIG. 7 is a graph of the activity of photocatalytic alkyl tertiary amines of examples 7, 9, 10 in the preparation of olefins.
The present invention is further illustrated by the following specific examples.
Example 1
(1) Preparation of lanthanum phosphate
Adding 3 mmol of La (NO)3)3·6H2O and 3 mmol (NH)4)2HPO4Each dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and mixing (NH)4)2HPO4The aqueous solution was slowly added dropwise to La (NO)3)3·6H2In an aqueous solution of O. Magnetically stirring for 1h at room temperature until a uniform colloid is formed, and transferring the colloid into a polytetrafluoroethylene lining. Putting the lining into a hydrothermal kettle, heating at 180 ℃ for 24 hours, naturally cooling to room temperature, washing the precipitate with distilled water for multiple times, and then vacuum-drying at 60 ℃ for 24 hours to obtain the product LaPO4And (4) nanorod powder.
（2）、Bi2WO6@LaPO4Preparation of
1mmol of Bi (NO)3)3·5H2O and 0.5 mmol Na2WO4·2H2O is respectively dissolved in 20 mL of deionized water; 0.05 g of LaPO was added4Adding Bi (NO) into the nanorod powder3)3·5H2Solution O and stirred for 1h, which is labeled solution A.
0.025g of cetyltrimethylammonium bromide was added to Na2WO4·2H2O solution and stirred for 1h, which is labeled B solution B.
Dropwise adding the solution A into the solution B under stirring, magnetically stirring the mixture at room temperature for 1h, transferring to a polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, keeping the temperature at 120 ℃ for 24h, and reactingWashing the yellow precipitate with deionized water for several times, and vacuum drying at 60 deg.C for 24 hr to obtain powdery product Bi2WO6@LaPO4-0.05 heterojunction material.
Example 2
(1) Preparation of lanthanum phosphate
Adding 3 mmol of La (NO)3)3·6H2O and 3 mmol (NH)4)2HPO4Each dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and mixing (NH)4)2HPO4The aqueous solution was slowly added dropwise to La (NO)3)3·6H2Magnetically stirring in O water solution at room temperature for 1 hr until uniform colloid is formed, transferring to polytetrafluoroethylene lining, heating the lining in hydrothermal kettle at 180 deg.C for 24 hr, naturally cooling to room temperature, washing precipitate with distilled water, and vacuum drying at 60 deg.C for 24 hr to obtain LaPO4And (4) nanorod powder.
（2）、Bi2WO6@LaPO4Preparation of
1mmol of Bi (NO)3)3·5H2O and 0.5 mmol Na2WO4·2H2O is respectively dissolved in 20 mL of deionized water; 0.1 g of LaPO was added4Adding Bi (NO) into the nanorod powder3)3·5H2Solution O and stirred for 1h, which is labeled solution A.
0.025g of cetyltrimethylammonium bromide was added to Na2WO4·2H2O solution and stirred for 1h, which is labeled B solution.
Dropwise adding the solution A into the solution B while stirring, magnetically stirring the mixture at room temperature for 1h, transferring to a polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, keeping the temperature at 120 ℃ for 24h, washing the yellow precipitate with deionized water for multiple times, and vacuum-drying at 60 ℃ for 24h to obtain a powdery product Bi2WO6@LaPO4-0.1 of a heterojunction material.
Example 3
(1) Preparation of lanthanum phosphate
Adding 3 mmol of La (NO)3)3·6H2O and 3 mmol (NH)4)2HPO4Each dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and mixing (NH)4)2HPO4The aqueous solution was slowly added dropwise to La (NO)3)3·6H2And magnetically stirring the mixture for 1 hour at room temperature in an O aqueous solution until a uniform colloid is formed, and then transferring the colloid into a polytetrafluoroethylene lining. Putting the lining into a hydrothermal kettle, heating at 180 ℃ for 24 hours, naturally cooling to room temperature, washing the precipitate with distilled water for multiple times, and then vacuum-drying at 60 ℃ for 24 hours to obtain a product LaPO4And (4) nanorod powder.
（2）、Bi2WO6@LaPO4Preparation of
1mmol of Bi (NO)3)3·5H2O and 0.5 mmol Na2WO4·2H2O is respectively dissolved in 20 mL of deionized water; 0.2 g of LaPO was added4Adding Bi (NO) into the nanorod powder3)3·5H2Solution O and stirred for 1h, which is labeled solution A.
0.025g of cetyltrimethylammonium bromide was added to Na2WO4·2H2O solution and stirred for 1h, which is labeled B solution.
Dropwise adding the solution A into the solution B while stirring, magnetically stirring the mixture at room temperature for 1h, transferring to a polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, keeping the temperature at 120 ℃ for 24h, washing the yellow precipitate with deionized water for multiple times, and vacuum-drying at 60 ℃ for 24h to obtain a powdery product Bi2WO6@LaPO4-0.2 of a heterojunction material.
Referring to the attached figure 1, the prepared heterojunction material is characterized by scanning of an electron microscope, and the two-dimensional flaky bismuth tungstate and the one-dimensional rod-shaped lanthanum phosphate are well combined together.
Referring to the attached figure 2, the prepared heterojunction material is characterized by electron microscope transmission, and the combination of two-dimensional sheet bismuth tungstate and one-dimensional rod lanthanum phosphate is very tight.
Referring to the attached figure 3, the prepared heterojunction material is characterized by X-ray diffraction, and no diffraction peak except for the two components of bismuth tungstate and lanthanum phosphate is observed in the heterojunction material, so that the crystal structures of the two components are not changed remarkably by the heterojunction material, and the purity of a sample is high.
Referring to the attached figure 4, the heterojunction material prepared in the above way is characterized by X-ray photoelectron spectroscopy, and five elements of Bi, O, W, La and P exist in the heterojunction material, so that the heterojunction material is successfully constructed.
Referring to the attached figure 5, the prepared heterojunction material is characterized by Raman spectrum, and the heterojunction material has Raman shift of two components, namely bismuth tungstate and lanthanum phosphate, so that the heterojunction material is successfully constructed.
Example 4
(1) Preparation of lanthanum phosphate
Adding 3 mmol of La (NO)3)3·6H2O and 3 mmol (NH)4)2HPO4Each dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and mixing (NH)4)2HPO4The aqueous solution was slowly added dropwise to La (NO)3)3·6H2In an aqueous solution of O. Magnetically stirring for 1h at room temperature until a uniform colloid is formed, and transferring the colloid into a polytetrafluoroethylene lining. The lining is put into a hydrothermal kettle and heated at 180 ℃ for 24 hours, and then naturally cooled to room temperature. Washing the precipitate with distilled water for several times, and vacuum drying at 60 deg.C for 24 hr to obtain LaPO4And (4) nanorod powder.
（2）、Bi2WO6@LaPO4Preparation of
1mmol of Bi (NO)3)3·5H2O and 0.5 mmol Na2WO4·2H2O is respectively dissolved in 20 mL of deionized water; 0.3 g of LaPO was added4Adding Bi (NO) into the nanorod powder3)3·5H2Solution O and stirred for 1h, which is labeled solution A.
0.025g of cetyltrimethylammonium bromide was added to Na2WO4·2H2In O solution and stirred for 1h, it is markedIs a B solution.
Dropwise adding the solution A into the solution B while stirring, magnetically stirring the mixture at room temperature for 1h, transferring the mixture into a polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, keeping the temperature at 120 ℃ for 24h, washing yellow precipitates for multiple times by deionized water, and then drying the yellow precipitates in vacuum at 60 ℃ for 24h to obtain a powdery product Bi2WO6@LaPO4-0.3 of a heterojunction material.
Example 5
(1) Preparation of lanthanum phosphate
Adding 3 mmol of La (NO)3)3·6H2O and 3 mmol (NH)4)2HPO4Each dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and mixing (NH)4)2HPO4The aqueous solution was slowly added dropwise to La (NO)3)3·6H2And magnetically stirring the mixture for 1 hour at room temperature in an O aqueous solution until a uniform colloid is formed, and then transferring the colloid into a polytetrafluoroethylene lining. Then the lining is put into a hydrothermal kettle and heated for 24 hours at the temperature of 180 ℃, then naturally cooled to room temperature, and the precipitate is washed by distilled water for a plurality of times and then dried for 24 hours in vacuum at the temperature of 60 ℃ to obtain the product LaPO4And (4) nanorod powder.
（2）、Bi2WO6@LaPO4Preparation of
1mmol of Bi (NO)3)3·5H2O and 0.5 mmol Na2WO4·2H2O is respectively dissolved in 20 mL of deionized water; 0.4 g of LaPO was added4Adding Bi (NO) into the nanorod powder3)3·5H2Solution O and stirred for 1h, which is labeled solution A.
0.025g of cetyltrimethylammonium bromide was added to Na2WO4·2H2O solution and stirred for 1h, which is labeled B solution.
The solution A was added dropwise to the solution B with stirring. Magnetically stirring the mixture at room temperature for 1h, transferring the mixture into a polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, keeping the temperature at 120 ℃ for 24h, washing yellow precipitate for multiple times by deionized water, and vacuum-drying at 60 ℃ for 24In hours, a powdery product of Bi is obtained2WO6@LaPO4-0.4 of a heterojunction material.
Bi prepared in example 32WO6@LaPO4-0.2 is catalyst, carbon dioxide is used as gas atmosphere, acetonitrile and water are used as solvent to carry out the photocatalytic reaction of alkyl tertiary amine for preparing olefin, the invention is further explained:
example 6
Adding acetonitrile/H into a quartz glass reactor2O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 32WO6@LaPO40.2 of heterojunction material and 0.1 mL of triethylamine. Before the illumination reaction, the reactor is vacuumized and degassed by a two-stage rotary vane pump, and pure CO is backfilled2The gas maintains the system pressure at atmospheric pressure. This degassing backfill was repeated three times. Throughout the experiment, the reactor was wrapped with aluminum foil to avoid light interference from the surrounding environment. The reaction time was 5 hours under light. A300W xenon lamp equipped with an ultraviolet cut-off filter (400-780 nm) was used as a light source, and the light intensity was fixed at 300 mW/cm2. After the end of the light irradiation, the gaseous product was analyzed by gas chromatography to determine the yield of ethylene to be 1.9. mu. mol/g/h.
Referring to FIG. 6, at 300 mW/cm2The triethylamine can be efficiently catalyzed to prepare the ethylene under the light intensity, and the yield of the ethylene is 1.9 mu mol/g/h.
Example 7
Adding acetonitrile/H into a quartz glass reactor2O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 32WO6@LaPO40.2 of heterojunction material and 0.1 mL of triethylamine. Before the illumination reaction, the reactor is vacuumized and degassed by a two-stage rotary vane pump, and pure CO is backfilled2The gas maintains the system pressure at atmospheric pressure. This degassing backfill was repeated three times. Throughout the experiment, the reactor was wrapped with aluminum foil to avoid light interference from the surrounding environment. The reaction time was 5 hours under light. A300W xenon lamp equipped with an ultraviolet cut-off filter (400 to 780 nm) is used as a light source,the light intensity is fixed at 400 mW/cm2. After the end of the light irradiation, the gaseous product was analyzed by gas chromatography, and the yield of ethylene was found to be 3.6. mu. mol/g/h.
Referring to FIG. 6, at 400 mW/cm2The triethylamine can be efficiently catalyzed to prepare the ethylene under the light intensity, and the yield of the ethylene is 3.6 mu mol/g/h.
Example 8
Adding acetonitrile/H into a quartz glass reactor2O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 32WO6@LaPO40.2 of heterojunction material and 0.1 mL of triethylamine. Before the illumination reaction, the reactor is vacuumized and degassed by a two-stage rotary vane pump, and pure CO is backfilled2The gas maintains the system pressure at atmospheric pressure. This degassing backfill was repeated three times. Throughout the experiment, the reactor was wrapped with aluminum foil to avoid light interference from the surrounding environment. The reaction time was 5 hours under light. A300W xenon lamp equipped with an ultraviolet cut-off filter (400 to 780 nm) was used as a light source, and the light intensity was fixed at 500 mW/cm2. After the end of the light irradiation, the gaseous product was analyzed by gas chromatography and the yield of ethylene was found to be 4. mu. mol/g/h.
Referring to FIGS. 6 to 7, at 500 mW/cm2The triethylamine can be efficiently catalyzed to prepare the ethylene under the light intensity, and the yield of the ethylene is 4 mu mol/g/h.
Example 9
Adding acetonitrile/H into a quartz glass reactor2O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 32WO6@LaPO40.2 of heterojunction material and 0.1 mL of tripropylamine. Before the illumination reaction, the reactor is vacuumized and degassed by a two-stage rotary vane pump, and pure CO is backfilled2The gas maintains the system pressure at atmospheric pressure. This degassing backfill was repeated three times. Throughout the experiment, the reactor was wrapped with aluminum foil to avoid light interference from the surrounding environment. The reaction time was 5 hours under light. A300W xenon lamp equipped with an ultraviolet cut-off filter (400 to 780 nm) was used as a light source, and the light intensity was fixed at 400 mW/cm2. After the illumination is finished, passing through the airThe gaseous product was analyzed by phase chromatography, and the yield of propylene was found to be 3. mu. mol/g/h.
Referring to FIG. 7, at 400 mW/cm2Under the light intensity, the tripropylamine can be effectively catalyzed to prepare the propylene, and the yield of the ethylene is 3 mu mol/g/h.
Example 10
Adding acetonitrile/H into a quartz glass reactor2O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 32WO6@LaPO40.2 of heterojunction material and 0.1 mL of diisopropylethylamine. Before the illumination reaction, the reactor is vacuumized and degassed by a two-stage rotary vane pump, and pure CO is backfilled2The gas maintains the system pressure at atmospheric pressure. This degassing backfill was repeated three times. Throughout the experiment, the reactor was wrapped with aluminum foil to avoid light interference from the surrounding environment. The reaction time was 5 hours under light. A300W xenon lamp equipped with an ultraviolet cut-off filter (400 to 780 nm) was used as a light source, and the light intensity was fixed at 400 mW/cm2. After the end of the light irradiation, the gaseous product was analyzed by gas chromatography, and it was found that the yield of ethylene was 1. mu. mol/g/h and the yield of propylene was 3.9. mu. mol/g/h.
Referring to FIG. 7, at 400 mW/cm2The catalyst can efficiently catalyze diisopropylethylamine to prepare ethylene and propylene under light intensity, the yield of the ethylene is 1 mu mol/g/h, and the yield of the propylene is 3.9 mu mol/g/h.
The above embodiments are only for further illustration of the present invention and are not intended to limit the present invention, and all equivalent implementations of the present invention should be included in the scope of the claims of the present invention.

Claims (2)

1. A preparation method of bismuth tungstate-lanthanum phosphate heterojunction material is characterized in that lanthanum phosphate and bismuth tungstate are adopted to synthesize Bi with a general formula2WO6@LaPO4-x, the specific preparation of which comprises the following steps:
a, step a: preparation of lanthanum phosphate
Will be (NH)4)2HPO4And La (NO)3)3·6H2O and dissociationThe ratio of the child water to the parent water is 1 mmol: 1-3 mmol: mixing 10-30 mL of the components according to a molar volume ratio, stirring the mixture to form uniform colloid, keeping the temperature at 25 ℃ for 1-24 hours, naturally cooling the mixture to room temperature after reaction, washing the precipitate with distilled water, and drying the precipitate at 50-80 ℃ for 10-24 hours to obtain a product LaPO4Nano-rod powder:
b, step (b): preparation of solution A
LaPO prepared by the method4Nanorod powder and Bi (NO)3)3·5H2O and deionized water were mixed at a ratio of 1 g: 2.5-20 mmol: mixing 10-30 mL of the mixture to obtain solution A;
c, step (c): preparation of solution B
Cetyl trimethyl ammonium bromide and Na2WO4·2H2O and deionized water 0.025 g: 2.5-20 mmol: mixing 10-30 mL of the mixture to obtain a solution B;
d, step: preparation of heterojunction materials
Dropwise adding the prepared solution A into the solution B, stirring and mixing, keeping the temperature at 120-180 ℃ for 12-24 hours, naturally cooling to room temperature after reaction, washing the precipitate with distilled water, and drying at 50-80 ℃ for 10-24 hours to obtain a powdery product, namely a bismuth tungstate-lanthanum phosphate heterojunction material with a general formula of Bi2WO6@LaPO4-x 。
2. The use of the bismuth tungstate-lanthanum phosphate heterojunction material prepared by the method as claimed in claim 1, wherein Bi is added2WO6@LaPO4-x is a catalyst, carbon dioxide is used as a gas atmosphere, acetonitrile and water are used as solvents to carry out photocatalytic reaction of alkyl tertiary amine for preparing olefin, and the molar volume ratio of the catalyst to the alkyl tertiary amine, the acetonitrile and the water is as follows: 1 mmol: 0.1-100 mmol: 0.1-100 mmol: 0.1-100 mL; the alkyl tertiary amine is triethylamine, tripropylamine, diisopropylethylamine or alkyl tertiary amine; the photocatalytic reaction time is 1-24 hours.
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