阅读说明：本技术 一种P掺杂WO3空心球负载ZnO纳米花光催化脱硫剂及制法 (P-doped WO3Hollow ball loaded ZnO nanoflower photocatalytic desulfurizer and preparation method thereof ) 是由 罗忠民 于 2020-12-31 设计创作，主要内容包括：本发明涉及光催化脱硫技术领域,且公开了一种P掺杂WO-3空心球负载ZnO纳米花光催化脱硫剂,三氧化钨生成纳米晶核,晶核生长成纳米球并组装成更大的空心球,P的掺杂引入晶格缺陷,拓宽了三氧化钨的光响应波段,硝酸锌首先形成晶核并逐渐生长成纳米片,纳米片逐渐组装成纳米花,三氧化钨与氧化锌形成异质结,当其受到光辐射时,氧化钨和氧化锌产生光生电子和空穴,由于三氧化钨的导带和价带低于氧化锌的导带,氧化锌导带上的光生电子会转移至三氧化钨的导带上,而三氧化钨价带上的空穴转移到氧化锌的价带上,使得光生电子和空穴分离,而空穴可以氧化水,生成羟基自由基,可以将噻吩等氧化,从而达到光催化脱硫的目的。(The invention relates to the technical field of photocatalytic desulfurization and discloses P-doped WO 3 The hollow sphere is loaded with ZnO nanoflower photocatalytic desulfurizer, tungsten trioxide generates nano crystal nuclei, the crystal nuclei grow into nanospheres and are assembled into larger hollow spheres, doping of P introduces lattice defects, the photoresponse waveband of tungsten trioxide is widened, zinc nitrate firstly forms the crystal nuclei and gradually grows into nanosheets, the nanosheets are gradually assembled into nanoflowers, tungsten trioxide and zinc oxide form a heterojunction, when the heterojunction is irradiated by light, tungsten oxide and zinc oxide generate photo-generated electrons and holes, because the conduction band and the valence band of the tungsten trioxide are lower than those of the zinc oxide, the photoproduction electrons on the conduction band of the zinc oxide can be transferred to the conduction band of the tungsten trioxide, and the holes on the valence band of tungsten trioxide are transferred to the valence band of zinc oxide, so that the photo-generated electrons and the holes are separated, the cavity can oxidize water to generate hydroxyl free radical and can oxidize thiophene and the like, thereby achieving the aim of photocatalytic desulfurization.)

1. P-doped WO₃The hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer is characterized in that: the P is doped with WO₃The preparation method of the hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer comprises the following steps:

(1) adding sodium tungstate and citric acid into a mixed solvent of deionized water and glycerol in a volume ratio of 10:2-6, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring to a reaction kettle, placing in an oven for hydrothermal reaction, cooling a product, washing with the deionized water and ethanol, drying after washing, transferring to a tubular furnace for calcining to obtain tungsten trioxide hollow spheres;

(2) adding the nano tungsten trioxide hollow spheres and sodium dihydrogen phosphate into a mixed solvent of deionized water and glacial acetic acid with the volume ratio of 10:2-4, stirring vigorously by ultrasonic waves for 4-8h, transferring the mixture into an oil bath pot for solvent thermal reaction, cooling a product, centrifuging, washing and drying the product, transferring the product into a tubular furnace for calcination to obtain phosphorus-doped nano tungsten trioxide hollow spheres and obtain a precursor of the phosphorus-doped nano tungsten trioxide hollow spheres;

(3) adding phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a deionized water solvent, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH of the solution to 8-9, transferring the solution into an oil bath pot, stirring the solution to perform a solvent thermal reaction, and removing the productRepeatedly washing and drying the seed water and the absolute ethyl alcohol, transferring the seed water and the absolute ethyl alcohol into a tube furnace for annealing treatment, and cooling the product to obtain the P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

2. P-doped WO according to claim 1₃The hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer is characterized in that: the mass ratio of the nano tungsten trioxide hollow spheres to the sodium dihydrogen phosphate in the step (2) is 100: 1-5.

3. P-doped WO according to claim 1₃The hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer is characterized in that: the temperature of the solvothermal reaction in the step (2) is 40-60 ℃, and the reaction time is 1-3 h.

4. P-doped WO according to claim 1₃The hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer is characterized in that: the calcining temperature in the step (2) is 400-500 ℃, and the calcining time is 2-6h in the nitrogen atmosphere.

5. P-doped WO according to claim 1₃The hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer is characterized in that: the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate in the step (3) is 100: 30-55.

6. P-doped WO according to claim 1₃The hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer is characterized in that: the temperature of the solvothermal reaction in the step (3) is 70-90 ℃, and the reaction is carried out for 10-15h by stirring.

7. P-doped WO according to claim 1₃The hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer is characterized in that: the temperature of the annealing treatment in the step (3) is 550-650 ℃, and the annealing is carried out for 1-3h in a nitrogen atmosphere.

Technical Field

The invention relates to the technical field of photocatalytic desulfurization, in particular to P-doped WO₃A hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer and a preparation method thereof.

Background

With the continuous development of global industrialization, the consumption rate of fossil energy is increased sharply, and the fossil energy contains a large amount of highly toxic and strongly corrosive sulfides such as thiophene, thioether and mercaptan, which seriously affect the use of the fossil energy and decompose the generated SO₂The common desulfurization technologies comprise hydrodesulfurization and adsorption desulfurization, and the photocatalytic oxidation desulfurization technology is a green technology with a great prospect, and can remove sulfides in the fossil fuel by oxidizing the sulfides in the fossil fuel, so that the aim of desulfurization is fulfilled.

The nano tungsten trioxide is a narrow-bandgap n-type semiconductor, can absorb visible light, and is widely applied to visible light response photocatalytic reaction at present, however, the common nano tungsten trioxide has a small specific surface area, a small number of photocatalytic desulfurization active sites on the surface, and the small specific surface area causes the low absorption efficiency of visible light, and cannot sufficiently absorb visible light, and when single nano tungsten trioxide is used as a photocatalytic desulfurizer, photoproduction electrons and cavities of the single nano tungsten trioxide are very easy to compound, and cannot meet the requirement of large-scale industrial application, so that the nano tungsten trioxide needs to be modified, on one hand, the morphology of the nano tungsten trioxide can be improved, on the other hand, the nano tungsten trioxide can be doped, the photoresponse frequency band of the nano tungsten trioxide can be improved, and the nano tungsten trioxide can be compounded with other inorganic semiconductor materials such as titanium dioxide and zinc oxide to form a heterojunction type photocatalytic desulfurizer, can effectively improve the photocatalytic desulfurization activity of the nano tungsten trioxide.

The nano zinc oxide is a wide-band gap semiconductor and has the advantages of low price, excellent photoelectric property, good photocatalytic property and the like, but the traditional nano zinc oxide has a small specific surface area and can only absorb ultraviolet light, and the traditional nano zinc oxide cannot effectively absorb sunlight with the ultraviolet light accounting for only 4 percent, so that the further application of the nano zinc oxide in the field of photocatalysis is limited, therefore, the nano zinc oxide is modified, the shape of the nano zinc oxide can be controlled by changing the preparation method, and the nano zinc oxide can also be compounded with inorganic semiconductors such as tin disulfide, tungsten trioxide and the like to form a unique heterojunction type photocatalytic desulfurizer, so that the photocatalytic desulfurization activity of the nano zinc oxide can be effectively improved.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a P-doped WO₃The hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer and the preparation method solve the problem of poor photocatalytic desulfurization activity of nano tungsten trioxide.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: p-doped WO₃The hollow sphere loads ZnO nanoflower photocatalysis desulfurizer, and the P is doped with WO₃The preparation method of the hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer comprises the following steps:

(1) adding a mixed solvent of deionized water and glycerol, sodium tungstate and citric acid in a volume ratio of 10:2-6 into a three-necked bottle, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, washing with deionized water and ethanol, drying after washing, transferring into a tubular furnace for calcining to obtain a tungsten trioxide hollow sphere;

(2) adding a mixed solvent of deionized water and glacial acetic acid, the nano tungsten trioxide hollow spheres and sodium dihydrogen phosphate in a volume ratio of 10:2-4 into a three-necked bottle, stirring vigorously by ultrasonic for 4-8h, transferring into an oil bath pot for solvent thermal reaction, cooling, centrifuging, washing and drying a product, transferring into a tubular furnace for calcination to obtain phosphorus-doped nano tungsten trioxide hollow spheres, and obtaining a precursor of the phosphorus-doped nano tungsten trioxide hollow spheres;

(3) adding a deionized water solvent, phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a three-necked bottle, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH of the solution to 8-9, transferring the solution into an oil bath pot, stirring the solution to perform a solvent thermal reaction, repeatedly washing and drying a product by using the deionized water and absolute ethyl alcohol, transferring the product into a tubular furnace for annealing treatment, and cooling the product to obtain PDoping of WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

Preferably, the mass ratio of the nano tungsten trioxide hollow spheres to the sodium dihydrogen phosphate in the step (2) is 100: 1-5.

Preferably, the temperature of the solvothermal reaction in the step (2) is 40-60 ℃, and the reaction time is 1-3 h.

Preferably, the calcination temperature in the step (2) is 400-500 ℃, and the calcination is carried out for 2-6h in a nitrogen atmosphere.

Preferably, the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate in the step (3) is 100: 30-55.

Preferably, the temperature of the solvothermal reaction in the step (3) is 70-90 ℃, and the reaction is carried out for 10-15h under stirring.

Preferably, the temperature of the annealing treatment in the step (3) is 550-650 ℃, and the annealing treatment is carried out for 1-3h in a nitrogen atmosphere.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the P-doped WO₃Hollow ball load ZnO nanoflower photocatalysis desulfurizer, hydrothermal method synthesis nanometer tungsten trioxide hollow ball in-process, at first generate tungsten trioxide nanometer crystal nucleus, the crystal nucleus grows gradually and becomes tungsten trioxide nanometer ball, along with hydrothermal reaction's going on, these tungsten trioxide nanometer ball assemble into bigger nanometer tungsten trioxide hollow ball gradually, the nanometer tungsten trioxide of this kind of hollow globular shape appearance has great specific surface area, more reaction active sites are provided for photocatalytic desulfurization, and simultaneously, great specific surface area can absorb more visible light, great improvement photocatalytic desulfurization rate and activity, in addition, P is with P⁵⁺The form of the nano tungsten trioxide hollow sphere is doped into the crystal lattice of the nano tungsten trioxide hollow sphere, so that the crystal lattice defect is introduced into the nano tungsten trioxide, the absorption edge of the nano tungsten trioxide is subjected to red shift, the photoresponse waveband of the nano tungsten trioxide hollow sphere is improved, the light absorption efficiency of the nano tungsten trioxide in a visible light area is further enhanced, and the photocatalytic desulfurization activity of the nano tungsten trioxide is effectively improved.

The P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer, in the process of synthesizing zinc oxide nanometer flower by a solvothermal method, zinc nitrate gradually forms zinc oxide crystal nucleus under the action of potassium hydroxide, the crystal nucleus gradually grows into zinc oxide nanometer sheet along with the continuous progress of reaction, the nanometer sheet is gradually assembled, finally zinc oxide nanometer flower is formed, the specific surface area of the nanometer zinc oxide is greatly improved due to the flower-shaped appearance, more active sites are provided for photocatalysis desulfurization, meanwhile, the contact area of the zinc oxide nanometer flower and light energy is greatly improved, the photocatalysis desulfurization activity of the nanometer zinc oxide is further improved, and the application range of the nanometer zinc oxide is widened.

The P-doped WO₃The hollow sphere loads a ZnO nanoflower photocatalytic desulfurizer, the phosphorus-doped nano tungsten trioxide hollow sphere and zinc oxide nanoflower form a unique heterojunction structure, when the composite photocatalytic desulfurizer is subjected to light radiation, the nano tungsten oxide and zinc oxide generate photoproduction electrons and holes, and because the positions of a conduction band and a valence band of the nano tungsten trioxide are lower than those of a conduction band of the zinc oxide, the photoproduction electrons on the conduction band of the nano zinc oxide are transferred to the conduction band of the nano tungsten trioxide, and the holes on the valence band of the nano tungsten trioxide are transferred to the valence band of the nano zinc oxide, so that the effective separation of the photoproduction electrons and the holes is realized, the holes on the valence band of the nano zinc oxide can oxidize water to generate hydroxyl radicals with strong oxidizing property, and sulfur derivatives such as thiophene can be oxidized into carbon dioxide, sulfur trioxide and water, and the aim of photocatalytic desulfurization is fulfilled.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: p-doped WO₃The preparation method of the hollow sphere loaded ZnO nanoflower photocatalytic desulfurizer comprises the following steps:

(1) adding a mixed solvent of deionized water and glycerol, sodium tungstate and citric acid in a volume ratio of 10:2-6 into a three-necked bottle, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, washing with deionized water and ethanol, drying after washing, transferring into a tubular furnace for calcining to obtain a tungsten trioxide hollow sphere;

(2) adding a mixed solvent of deionized water and glacial acetic acid, a nano tungsten trioxide hollow sphere and sodium dihydrogen phosphate into a three-neck bottle in a volume ratio of 10:2-4, wherein the mass ratio of the nano tungsten trioxide hollow sphere to the sodium dihydrogen phosphate is 100:1-5, stirring vigorously by ultrasonic waves for 4-8h, transferring the mixture into an oil bath pot, carrying out solvothermal reaction at 40-60 ℃ for 1-3h, cooling the product, centrifuging, washing and drying the product, transferring the product into a tubular furnace, and calcining the product at 400-500 ℃ for 2-6h in a nitrogen atmosphere to obtain a phosphorus-doped nano tungsten trioxide hollow sphere precursor;

(3) adding a deionized water solvent, phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a three-neck flask, wherein the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate is 100:30-55, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH value of the solution to 8-9, transferring the solution into an oil bath pot, stirring the solution at 70-90 ℃ to react for 10-15h, repeatedly washing and drying the product with deionized water and absolute ethyl alcohol, transferring the product into a tubular furnace, annealing the product at 550-650 ℃ in a nitrogen atmosphere for 1-3h, and cooling the product to obtain P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

Example 1

(1) Adding a deionized water and glycerol mixed solvent, sodium tungstate and citric acid in a volume ratio of 10:2 into a three-necked bottle, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, washing with deionized water and ethanol, drying after washing, transferring into a tubular furnace for calcining, and thus obtaining tungsten trioxide hollow spheres;

(2) adding a deionized water and glacial acetic acid mixed solvent, a nano tungsten trioxide hollow sphere and sodium dihydrogen phosphate into a three-necked bottle in a volume ratio of 10:2, wherein the mass ratio of the nano tungsten trioxide hollow sphere to the sodium dihydrogen phosphate is 100:1, stirring vigorously by ultrasonic for 4h, transferring the mixture into an oil bath pot, carrying out solvothermal reaction at 40 ℃ for 1h, cooling the product, centrifuging, washing and drying the product, transferring the product into a tubular furnace, and calcining the product at 400 ℃ for 2h in a nitrogen atmosphere to obtain a phosphorus-doped nano tungsten trioxide hollow sphere precursor;

(3) adding a deionized water solvent, phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a three-neck bottle, wherein the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate is 100:30, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH of the solution to 8, transferring the solution into an oil bath pot, stirring the solution at 70 ℃ for reaction for 10 hours, repeatedly washing and drying a product by using deionized water and absolute ethyl alcohol, transferring the product into a tubular furnace, annealing the product at 550 ℃ for 1 hour in a nitrogen atmosphere, and cooling the product to obtain P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

Example 2

(1) Adding a deionized water and glycerol mixed solvent, sodium tungstate and citric acid in a volume ratio of 10:3 into a three-necked bottle, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, washing with deionized water and ethanol, drying after washing, transferring into a tubular furnace for calcining, and thus obtaining tungsten trioxide hollow spheres;

(2) adding a mixed solvent of deionized water and glacial acetic acid, a nano tungsten trioxide hollow sphere and sodium dihydrogen phosphate into a three-necked bottle in a volume ratio of 10:2.5, wherein the mass ratio of the nano tungsten trioxide hollow sphere to the sodium dihydrogen phosphate is 100:2.3, stirring vigorously by ultrasonic waves for 5h, transferring the mixture into an oil bath pot, carrying out solvothermal reaction at 45 ℃ for 1.5h, cooling the product, centrifuging, washing and drying, transferring the product into a tubular furnace, and calcining the product at 420 ℃ for 3h in a nitrogen atmosphere to obtain a phosphorus-doped nano tungsten trioxide hollow sphere precursor;

(3) adding deionized water solvent, phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a three-mouth bottle, wherein the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate is 100:38, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH value of the solution to 8, transferring the solution into an oil bath pot, stirring the solution at 75 ℃ to react for 12 hours, repeatedly washing and drying the product with deionized water and absolute ethyl alcohol, transferring the product into a tubular furnaceAnnealing treatment is carried out for 1.5h at 580 ℃ in nitrogen atmosphere, and the product is cooled to obtain P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

Example 3

(1) Adding a mixed solvent of deionized water and glycerol, sodium tungstate and citric acid in a volume ratio of 10:4.5 into a three-necked bottle, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, washing with deionized water and ethanol, drying after washing, transferring into a tubular furnace for calcining to obtain a tungsten trioxide hollow sphere;

(2) adding a mixed solvent of deionized water and glacial acetic acid, a nano tungsten trioxide hollow sphere and sodium dihydrogen phosphate into a three-mouth bottle in a volume ratio of 10:3.5, wherein the mass ratio of the nano tungsten trioxide hollow sphere to the sodium dihydrogen phosphate is 100:3.6, stirring vigorously by ultrasonic waves for 6 hours, transferring the mixture into an oil bath pot, carrying out solvothermal reaction at 50 ℃ for 2 hours, cooling the product, centrifuging, washing and drying, transferring the product into a tubular furnace, and calcining the product at 450 ℃ for 4 hours in a nitrogen atmosphere to obtain a phosphorus-doped nano tungsten trioxide hollow sphere precursor;

(3) adding a deionized water solvent, phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a three-neck bottle, wherein the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate is 100:46, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH of the solution to 9, transferring the solution into an oil bath pot, stirring the solution at 85 ℃ for reaction for 14 hours, repeatedly washing and drying a product by using deionized water and absolute ethyl alcohol, transferring the product into a tubular furnace, annealing the product at 600 ℃ for 2.5 hours in a nitrogen atmosphere, and cooling the product to obtain P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

Example 4

(1) Adding a mixed solvent of deionized water and glycerol, sodium tungstate and citric acid in a volume ratio of 10:6 into a three-necked bottle, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, washing with deionized water and ethanol, drying after washing, transferring into a tubular furnace for calcining, and thus obtaining tungsten trioxide hollow spheres;

(2) adding a deionized water and glacial acetic acid mixed solvent, a nano tungsten trioxide hollow sphere and sodium dihydrogen phosphate into a three-necked bottle in a volume ratio of 10:4, wherein the mass ratio of the nano tungsten trioxide hollow sphere to the sodium dihydrogen phosphate is 100:5, carrying out ultrasonic vigorous stirring for 8 hours, transferring the mixture into an oil bath pot, carrying out solvothermal reaction for 3 hours at the temperature of 60 ℃, cooling, centrifuging, washing and drying a product, transferring the product into a tubular furnace, and calcining the product for 6 hours at the temperature of 500 ℃ in a nitrogen atmosphere to obtain a phosphorus-doped nano tungsten trioxide hollow sphere precursor;

(3) adding a deionized water solvent, phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a three-neck bottle, wherein the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate is 100:55, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH of the solution to 9, transferring the solution into an oil bath pot, stirring the solution at 90 ℃ for reaction for 15 hours, repeatedly washing and drying a product by using deionized water and absolute ethyl alcohol, transferring the product into a tubular furnace, annealing the product at 650 ℃ for 3 hours in a nitrogen atmosphere, and cooling the product to obtain P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

Comparative example 1

(1) Adding a mixed solvent of deionized water and glycerol, sodium tungstate and citric acid in a volume ratio of 10:1 into a three-necked bottle, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, washing with deionized water and ethanol, drying after washing, transferring into a tubular furnace for calcining, and thus obtaining tungsten trioxide hollow spheres;

(2) adding a deionized water and glacial acetic acid mixed solvent, a nano tungsten trioxide hollow sphere and sodium dihydrogen phosphate into a three-mouth bottle in a volume ratio of 10:1, wherein the mass ratio of the nano tungsten trioxide hollow sphere to the sodium dihydrogen phosphate is 100:0.1, stirring vigorously by ultrasonic waves for 2h, transferring the mixture into an oil bath pot, carrying out solvothermal reaction at 40 ℃ for 2h, cooling the product, centrifuging, washing and drying, transferring the product into a tubular furnace, and calcining the product at 400 ℃ for 1h in a nitrogen atmosphere to obtain a phosphorus-doped nano tungsten trioxide hollow sphere and obtain a precursor of the phosphorus-doped nano tungsten trioxide hollow sphere;

(3) adding a deionized water solvent, phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a three-neck bottle, wherein the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate is 100:22, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH of the solution to 8, transferring the solution into an oil bath pot, stirring the solution at 70 ℃ for reaction for 8 hours, repeatedly washing and drying a product by using deionized water and absolute ethyl alcohol, transferring the product into a tubular furnace, annealing the product at 550 ℃ for 0.5 hour in a nitrogen atmosphere, and cooling the product to obtain P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

Comparative example 2

(1) Adding a deionized water and glycerol mixed solvent, sodium tungstate and citric acid in a volume ratio of 10:7 into a three-necked bottle, ultrasonically stirring uniformly, adding hydrochloric acid, uniformly mixing, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, washing with deionized water and ethanol, drying after washing, transferring into a tubular furnace for calcining, and thus obtaining tungsten trioxide hollow spheres;

(2) adding a deionized water and glacial acetic acid mixed solvent, a nano tungsten trioxide hollow sphere and sodium dihydrogen phosphate into a three-mouth bottle in a volume ratio of 10:6, wherein the mass ratio of the nano tungsten trioxide hollow sphere to the sodium dihydrogen phosphate is 100:6.3, stirring vigorously by ultrasonic waves for 10 hours, transferring the mixture into an oil bath pot, carrying out solvothermal reaction at 60 ℃ for 4 hours, cooling the product, centrifuging, washing and drying, transferring the product into a tubular furnace, and calcining the product at 500 ℃ for 8 hours in a nitrogen atmosphere to obtain a phosphorus-doped nano tungsten trioxide hollow sphere and obtain a precursor of the phosphorus-doped nano tungsten trioxide hollow sphere;

(3) adding a deionized water solvent, phosphorus-doped nano tungsten trioxide hollow spheres and zinc nitrate into a three-neck bottle, wherein the mass ratio of the phosphorus-doped nano tungsten trioxide hollow spheres to the zinc nitrate is 100:63, adding potassium hydroxide after uniform ultrasonic dispersion, adjusting the pH value of the solution to 9, transferring the solution into an oil bath pot, stirring the solution at 90 ℃ for reacting for 18 hours, repeatedly washing and drying a product by using deionized water and absolute ethyl alcohol, transferring the product into a tubular furnace, and performing nitrogen atmosphere treatment to obtain the productAnnealing at 650 ℃ for 5h, cooling the product to obtain P-doped WO₃The hollow sphere loads ZnO nanometer flower photocatalysis desulfurizer.

Adding thiophene into n-octane solution to prepare simulated oil with the sulfur content of 500mg/L, and adding the simulated oil and P-doped WO with the concentration of 25mg/L into a reactor₃The hollow sphere is loaded with ZnO nanoflower photocatalytic desulfurizer, hydrogen peroxide and methanol extractant are added, a 350W xenon lamp is used as a light source to radiate the light source for 30min, a UV2401 ultraviolet spectrophotometer is used to test the absorbance of thiophene in the solution, and the desulfurization rate is calculated.