CN113083335B - 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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CN113083335B
CN113083335B CN202110306111.5A CN202110306111A CN113083335B CN 113083335 B CN113083335 B CN 113083335B CN 202110306111 A CN202110306111 A CN 202110306111A CN 113083335 B CN113083335 B CN 113083335B
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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 formula 2 WO 6 @LaPO 4 -x of a powdered heterojunction material; adding Bi 2 WO 6 @LaPO 4 Under 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 method has the advantages of high catalytic activity, simple preparation, easily obtained raw materials, low production cost, high yield, environmental friendliness and wide application prospect when being used for preparing corresponding olefin by photocatalytic 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 the 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 TiO 2 Since 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, Bi 2 WO 6 It has been extensively studied due to its narrow bandgap (2.58eV), high stability and low cost. However, Bi 2 WO 6 The photocatalytic performance of (a) is significantly limited by the rapid recombination rate of electron-hole pairs. And lanthanum phosphate (LaPO) 4 ) The conduction band has a longer carrier lifetime and stronger reduction capability, but the forbidden band is very wide and is difficult to be excited by visible light, so the research progress of the conduction band 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 Bi 2 WO 6 @LaPO 4 -x powdered heterojunction material of Bi 2 WO 6 @LaPO 4 The-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 preparation method of bismuth tungstate-lanthanum phosphate heterojunction material is characterized by adoptingSynthesizing general formula Bi by using lanthanum phosphate and bismuth tungstate 2 WO 6 @LaPO 4 -x, the specific preparation of which comprises the following steps:
a, step: preparation of lanthanum phosphate
Will be (NH) 4 ) 2 HPO 4 And La (NO) 3 ) 3 ·6H 2 O and deionized water in a ratio of 1 mmol: 1-3 mmol: mixing 10-30 mL of the mixture 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 LaPO 4 And (4) nanorod powder.
b, step (b): preparation of solution A
LaPO prepared by the method 4 Nanorod powder and Bi (NO) 3 ) 3 ·5H 2 O 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 Na 2 WO 4 ·2H 2 O and deionized water 0.025 g: 2.5-20 mmol: 10-30 mL of the solution 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 Bi 2 WO 6 @LaPO 4 -x 。
The application of bismuth tungstate-lanthanum phosphate heterojunction material is characterized by that Bi is added 2 WO 6 @LaPO 4 -x is a catalyst, carbon dioxide is used as a gas atmosphere, acetonitrile and water are used as solvents to carry out a photocatalytic reaction for preparing olefin from alkyl tertiary amine, 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 alkylA 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 Bi 2 WO 6 @LaPO 4 The powder catalyst of-x has simple method and wide application prospect.
2) Using the Bi 2 WO 6 @LaPO 4 -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 ·6H 2 O and 3 mmol (NH) 4 ) 2 HPO 4 Each dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and dissolving (NH) 4 ) 2 HPO 4 The aqueous solution was slowly added dropwise to La (NO) 3 ) 3 ·6H 2 In 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 and adding the lining at the temperature of 180 DEG CHeating 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 LaPO product 4 And (4) nanorod powder.
（2）、Bi 2 WO 6 @LaPO 4 Preparation of (2)
1mmol of Bi (NO) 3 ) 3 ·5H 2 O and 0.5 mmol Na 2 WO 4 ·2H 2 O is respectively dissolved in 20 mL of deionized water; 0.05 g of LaPO was added 4 Adding Bi (NO) into the nanorod powder 3 ) 3 ·5H 2 Solution O and stirred for 1h, which is labeled solution A.
0.025 g of cetyltrimethylammonium bromide was added to Na 2 WO 4 ·2H 2 O solution and stirred for 1h, which is labeled B solution B.
Dropwise adding the solution A into the solution B while stirring, magnetically stirring the mixture at room temperature for 1h, transferring the mixture to a polytetrafluoroethylene lining, placing the lining into a hydrothermal kettle, keeping the temperature at 120 ℃ for 24h, washing yellow precipitates for many times by deionized water after reaction, and performing vacuum drying at 60 ℃ for 24h to obtain a powdery product Bi 2 WO 6 @LaPO 4 -0.05 heterojunction material.
Example 2
(1) Preparation of lanthanum phosphate
Adding 3 mmol of La (NO) 3 ) 3 ·6H 2 O and 3 mmol (NH) 4 ) 2 HPO 4 Each was dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and dissolving (NH) 4 ) 2 HPO 4 The aqueous solution was slowly added dropwise to La (NO) 3 ) 3 ·6H 2 Magnetically 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 LaPO 4 And (4) nanorod powder.
（2）、Bi 2 WO 6 @LaPO 4 Preparation of
1mmol of Bi (NO) 3 ) 3 ·5H 2 O and 0.5 mmol Na 2 WO 4 ·2H 2 O is respectively dissolved in 20 mL of deionized water; 0.1 g of LaPO was added 4 Adding Bi (NO) into the nanorod powder 3 ) 3 ·5H 2 Solution O and stirred for 1h, which is labeled solution A.
0.025 g of cetyltrimethylammonium bromide was added to Na 2 WO 4 ·2H 2 O solution and stirred for 1h, which is labeled B solution.
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, washing yellow precipitate with deionized water for multiple times, and drying in vacuum at 60 ℃ for 24h to obtain a powdery product Bi 2 WO 6 @LaPO 4 -0.1 of a heterojunction material.
Example 3
(1) Preparation of lanthanum phosphate
Adding 3 mmol of La (NO) 3 ) 3 ·6H 2 O and 3 mmol (NH) 4 ) 2 HPO 4 Each dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and mixing (NH) 4 ) 2 HPO 4 The aqueous solution was slowly added dropwise to La (NO) 3 ) 3 ·6H 2 And 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 LaPO 4 And (4) nanorod powder.
（2）、Bi 2 WO 6 @LaPO 4 Preparation of
1mmol of Bi (NO) 3 ) 3 ·5H 2 O and 0.5 mmol Na 2 WO 4 ·2H 2 O is respectively dissolved in 20 mL of deionized water; 0.2 g of LaPO was added 4 Adding Bi (NO) into the nanorod powder 3 ) 3 ·5H 2 O solutionAnd stirred for 1h, which is labeled as solution a.
0.025 g of cetyltrimethylammonium bromide was added to Na 2 WO 4 ·2H 2 O 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 Bi 2 WO 6 @LaPO 4 -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 ·6H 2 O and 3 mmol (NH) 4 ) 2 HPO 4 Each was dissolved in 35 mL of deionized water and stirred to form a clear solution. Under stirring will be (NH 4 ) 2 HPO 4 The aqueous solution was slowly added dropwise to La (NO) 3 ) 3 ·6H 2 In 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 LaPO 4 And (4) nanorod powder.
（2）、Bi 2 WO 6 @LaPO 4 Preparation of (2)
1mmol of Bi (NO) 3 ) 3 ·5H 2 O and 0.5 mmol Na 2 WO 4 ·2H 2 O is respectively dissolved in 20 mL of deionized water; 0.3 g of LaPO was added 4 Nanorod powder added with Bi (NO) 3 ) 3 ·5H 2 Solution O and stirred for 1h, which is labeled solution A.
0.025 g of cetyltrimethylammonium bromide was added to Na 2 WO 4 ·2H 2 O solution and stirred for 1h, which is labeled as 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 Bi 2 WO 6 @LaPO 4 -0.3 heterojunction material.
Example 5
(1) Preparation of lanthanum phosphate
Adding 3 mmol of La (NO) 3 ) 3 ·6H 2 O and 3 mmol (NH) 4 ) 2 HPO 4 Each dissolved in 35 mL of deionized water and stirred to form a clear solution. Stirring and mixing (NH) 4 ) 2 HPO 4 The aqueous solution was slowly added dropwise to La (NO) 3 ) 3 ·6H 2 And 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 cooling to room temperature, washing the precipitate with distilled water for many times, and then drying in vacuum for 24 hours at the temperature of 60 ℃ to obtain the product LaPO 4 And (4) nano rod powder.
（2）、Bi 2 WO 6 @LaPO 4 Preparation of
1mmol of Bi (NO) 3 ) 3 ·5H 2 O and 0.5 mmol Na 2 WO 4 ·2H 2 O is respectively dissolved in 20 mL of deionized water; 0.4 g of LaPO was added 4 Adding Bi (NO) into the nanorod powder 3 ) 3 ·5H 2 O solution and stir for 1h, which is labeled A solution.
0.025 g of cetyltrimethylammonium bromide was added to Na 2 WO 4 ·2H 2 O 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 then drying the yellow precipitate in vacuum at 60 ℃ for 24h to obtain a powdery product Bi 2 WO 6 @LaPO 4 -0.4 of a heterojunction material.
Bi prepared in example 3 2 WO 6 @LaPO 4 -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 reactor 2 O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 3 2 WO 6 @LaPO 4 0.2 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 backfilled 2 The 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. Equipped with ultraviolet cut-offA300W xenon lamp with a filter (400-780 nm) was used as the light source, and the light intensity was fixed at 300 mW/cm 2 . 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/cm 2 The 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 reactor 2 O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 3 2 WO 6 @LaPO 4 0.2 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 backfilled 2 The 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/cm 2 . 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/cm 2 The 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 reactor 2 O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 3 2 WO 6 @LaPO 4 0.2 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 backfilled 2 The 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 500 mW/cm 2 . 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/cm 2 The 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 reactor 2 O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 3 2 WO 6 @LaPO 4 0.2 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 backfilled 2 The 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) is used as a light source, and the light intensity is fixed at 400 mW/cm 2 . After the end of the light irradiation, the gaseous product was analyzed by gas chromatography, and the yield of propylene was found to be 3. mu. mol/g/h.
Referring to FIG. 7, at 400 mW/cm 2 Under 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 reactor 2 O (4: 1, 10 mL), followed by the sequential addition of 20 mg of Bi prepared in example 3 2 WO 6 @LaPO 4 0.2 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 backfilled 2 The 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/cm 2 . End of illuminationThereafter, the gaseous product was analyzed by gas chromatography to find 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/cm 2 The 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 (4)

1. A preparation method of bismuth tungstate-lanthanum phosphate heterojunction material for synthesizing olefin by photocatalytic alkyl tertiary amine is characterized in that lanthanum phosphate and bismuth tungstate are adopted to synthesize Bi with a general formula 2 WO 6 @LaPO 4 -x, which is prepared in the following steps:
a, step a: preparation of lanthanum phosphate
Adding 3 mmol of La (NO) 3 ) 3 ·6H 2 O and 3 mmol (NH) 4 ) 2 HPO 4 Respectively dissolved in 35 mL of deionized water and stirred to form transparent solutions, and (NH) is added under stirring 4 ) 2 HPO 4 The aqueous solution was slowly added dropwise to La (NO) 3 ) 3 ·6H 2 Magnetically stirring for 1h at room temperature in an O aqueous solution until a uniform colloid is formed, and transferring the uniform 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 LaPO 4 Nano rod powder;
b, step (a): preparation of solution A
1mmol of Bi (NO) 3 ) 3 ·5H 2 O and 0.5 mmol Na 2 WO 4 ·2H 2 O is respectively dissolved in 20 mL of deionized water; 0.05 g of LaPO was added 4 Adding Bi (NO) into the nanorod powder 3 ) 3 ·5H 2 Stirring the solution O for 1 hour, and marking the solution O as solution A;
c, step (c): preparation of solution B
0.025 g of cetyltrimethylammonium bromide was added to Na 2 WO 4 ·2H 2 Stirring in the O solution for 1h, and marking as a B solution;
d, step: preparation of heterojunction materials
Dropwise adding the solution A into the solution B while stirring, magnetically stirring the mixture at room temperature for 1h, transferring the mixture to 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 after reaction, and then drying the yellow precipitates in vacuum at 60 ℃ for 24h to obtain a powdery product Bi 2 WO 6 @LaPO 4 -0.05 heterojunction material.
2. A preparation method of bismuth tungstate-lanthanum phosphate heterojunction material for synthesizing olefin by photocatalytic alkyl tertiary amine is characterized in that lanthanum phosphate and bismuth tungstate are adopted to synthesize Bi with a general formula 2 WO 6 @LaPO 4 -x, which is prepared in the following steps:
a, step a: preparation of lanthanum phosphate
Adding 3 mmol of La (NO) 3 ) 3 ·6H 2 O and 3 mmol (NH) 4 ) 2 HPO 4 Respectively dissolved in 35 mL of deionized water and stirred to form transparent solutions, and (NH) is added under stirring 4 ) 2 HPO 4 The aqueous solution was slowly added dropwise to La (NO) 3 ) 3 ·6H 2 Magnetically stirring for 1h at room temperature in an O aqueous solution until a uniform colloid is formed, and transferring the uniform 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 LaPO 4 Nano rod powder;
b, step (b): preparation of solution A
1mmol of Bi (NO) 3 ) 3 ·5H 2 O and 0.5 mmol Na 2 WO 4 ·2H 2 O is respectively dissolved in 20 mL of deionized water; 0.1 g of LaPO was added 4 Adding Bi (into the nanorod powder)NO 3 ) 3 ·5H 2 Stirring the solution O for 1 hour, and marking the solution O as solution A;
c, step (c): preparation of solution B
0.025 g of cetyltrimethylammonium bromide was added to Na 2 WO 4 ·2H 2 Stirring in the O solution for 1h, and marking as a B solution;
d, step: preparation of heterojunction materials
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 Bi 2 WO 6 @LaPO 4 -0.1 of a heterojunction material.
3. A preparation method of bismuth tungstate-lanthanum phosphate heterojunction material for synthesizing olefin by photocatalytic alkyl tertiary amine is characterized in that lanthanum phosphate and bismuth tungstate are adopted to synthesize Bi with a general formula 2 WO 6 @LaPO 4 -x, specifically prepared by the following steps:
a, step a: preparation of lanthanum phosphate
Adding 3 mmol of La (NO) 3 ) 3 ·6H 2 O and 3 mmol (NH) 4 ) 2 HPO 4 Respectively dissolved in 35 mL of deionized water and stirred to form transparent solutions, and (NH) is added under stirring 4 ) 2 HPO 4 The aqueous solution was slowly added dropwise to La (NO) 3 ) 3 ·6H 2 Magnetically stirring for 1h 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 LaPO 4 Nano-rod powder;
b, step (b): preparation of solution A
1mmol of Bi (NO) 3 ) 3 ·5H 2 O and 0.5 mmol Na 2 WO 4 ·2H 2 O is respectively dissolved in 20 mL of deionized water; 0.2 g of LaPO was added 4 Adding Bi (NO) into the nanorod powder 3 ) 3 ·5H 2 Stirring the solution O for 1 hour, and marking the solution O as solution A;
c, step (c): preparation of solution B
0.025 g of cetyltrimethylammonium bromide was added to Na 2 WO 4 ·2H 2 Stirring for 1h in the O solution, wherein the mark is B solution;
d, step: preparation of heterojunction materials
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 Bi 2 WO 6 @LaPO 4 -0.2 of a heterojunction material.
4. The application of the bismuth tungstate-lanthanum phosphate heterojunction material prepared by the preparation method of the bismuth tungstate-lanthanum phosphate heterojunction material for synthesizing olefin by photocatalytic alkyl tertiary amine as claimed in claim 1, which is characterized in that lanthanum phosphate and bismuth tungstate are synthesized into a material with a general formula of Bi 2 WO 6 @LaPO 4 -x, taking a powder heterojunction material as a catalyst, and carrying out a photocatalytic reaction for preparing olefin by using tertiary alkyl amine by using carbon dioxide as a gas atmosphere and acetonitrile and water as solvents, wherein the molar volume ratio of the catalyst to the tertiary alkyl 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 or diisopropylethylamine; the photocatalytic reaction time is 1-24 hours.
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