Rare earth la-anchored ws2 / wo3-x heterojunction photocatalytic material, preparation method and application

Abstract

The application provides a rare earth La-anchored WS2 / WO 3‑x The application discloses a heterojunction photocatalytic material, a preparation method and application. 3‑x The application discloses a heterojunction precursor, a certain amount of the precursor WS2 / WO 3‑x The application discloses a rare earth single atom La-anchored WS2 / WO 3‑x The application discloses a heterojunction photocatalytic material. The application can solve the problem of low catalytic activity caused by fast recombination of photo-generated carriers in the traditional WO3 material photocatalytic process, and further improves the activity of photocatalytic nitrogen hydrogenation conversion into product ammonia.

Description

Technical Field

[0001] This invention relates to the field of photocatalytic materials, and particularly to a rare-earth La-anchored WS2 / WO material. 3-x Heterojunction photocatalytic materials, preparation methods and applications. Background Technology

[0002] Ammonia (NH3) is an important inorganic industrial chemical. Currently, the most commonly used and mature industrial method is the Haber-Bosch process. However, due to the high bond energy of the N2 molecule, the reaction conditions are harsh, requiring high temperature and pressure for synthesis, resulting in huge energy consumption and the emission of large amounts of greenhouse gases. Therefore, there is an urgent need for a new method to fix N2 under mild conditions. Currently, various methods exist, including enzyme catalysis, photocatalysis, electrocatalysis, and photoelectrocatalysis. Among them, photocatalytic nitrogen fixation has become a new method of attention and research in recent years due to its low cost and environmental friendliness. In the photocatalytic nitrogen fixation reaction, the adsorption and activation of N2 is a crucial process. Studies have shown that vacancy engineering can serve as adsorption active sites, adjusting the electronic structure of the catalyst and the migration of photogenerated charges.

[0003] Rare earth elements are known as "industrial vitamins" due to their unique electronic structure and excellent optical, electromagnetic, and physical properties. Recent studies have shown that rare earth elements have a significant impact on improving the performance of ammonia catalytic synthesis, thus demonstrating their great potential in this area. However, current research on rare earth single-atom catalysts for photocatalytic nitrogen fixation is limited. Summary of the Invention

[0004] In view of the above, the main objective of this invention is to propose a rare earth La anchoring WS2 / WO method. 3-x Heterojunction photocatalytic materials, preparation methods, and applications are proposed to address the aforementioned technical problems.

[0005] This invention proposes a rare earth La-anchored WS2 / WO method. 3-x Heterojunction photocatalytic materials, with WS2 / WO 3-x As a matrix, rare earth element La is doped into its lattice, wherein La is dispersed in the form of single atoms, and the rare earth element La and WS2 / WO 3-x The mass ratio is 0.01 to 0.05:1.

[0006] This invention proposes a rare earth La-anchored WS2 / WO method. 3-x The method for preparing heterojunction photocatalytic materials, used to prepare the above-mentioned rare earth La-anchored WS2 / WO 3-x Heterojunction photocatalytic materials, wherein the method includes the following steps:

[0007] Step 1: Preparation of WS2 nanosheets by ultrasonic exfoliation:

[0008] Tungsten disulfide and an intercalating agent were added to a beaker to obtain a mixed solution. The mixed solution was subjected to ultrasonic treatment to exfoliate the tungsten disulfide into nanosheets. The ultrasonic mixed solution was separated by centrifugation, and the product was collected to obtain the exfoliated nanosheets. The exfoliated nanosheets were then vacuum dried to obtain dark gray WS2 nanosheets.

[0009] Step 2: In-situ hydrothermal preparation of heterojunction WS2 / WO 3-x :

[0010] H2WO4 and WCl6 were added to anhydrous ethanol and stirred for time c. After stirring for time d, the exfoliated WS2 nanosheets were added and stirring was continued for time d. After stirring, the mixture was transferred to a reaction vessel lined with polytetrafluoroethylene and heated hydrothermally at temperature e for time f. After cooling to room temperature, the mixture was washed several times with anhydrous ethanol and dried in a vacuum oven at temperature g for time h to obtain the powdered WS2 / WO3 precursor.

[0011] Step 3: Prepare oxygen-vacancy-rich rare-earth single-atom La-anchored oxygen-vacancy-rich WS2 / WO by high-temperature hydrogen reduction. 3-x Heterojunction photocatalytic materials:

[0012] The prepared WS2 / WO3 powder and lanthanum nitrate hexahydrate were ground in a mortar for i time. After grinding, the powder was placed in a magnetic boat and calcined in a tube furnace at temperature j for k time under a mixed gas atmosphere of H2 / N2 to obtain rare earth La-anchored WS2 / WO3. 3-x Heterojunction photocatalytic materials.

[0013] Furthermore, in step 1, the amount of tungsten disulfide is 0.1–0.3 g, the intercalating agent is N-methylpyrrolidone, and the preset volume of N-methylpyrrolidone is 70–100 mL.

[0014] Furthermore, in step 2, the mass of H2WO4 is 1-3g, the mass of WCl6 is 0.1-0.3g, the mass of WS2 nanosheets is 0.1-0.3g, and the preset volume of anhydrous ethanol is 30-50mL.

[0015] Furthermore, in step 2, the mass ratio of WS2 to H2WO4 is 1:10.

[0016] Furthermore, in step 3, the mass of WS2 / WO3 powder is 2g, and the mass of lanthanum nitrate hexahydrate is 0.02-0.1g.

[0017] Furthermore, time a is 5h, centrifugation speed is 7500r / min, time c is 10min, time d is 20min, temperature e is 100℃, time f is 24h, temperature g is 60℃, time h is 8h, time i is 10min, temperature j is 500℃, and time k is 3h.

[0018] Furthermore, in step 2, the H2 content in the H2 / N2 mixture is 10%.

[0019] A rare earth La anchoring WS2 / WO 3-x Applications of heterojunction photocatalytic materials, using the above-mentioned preparation method to prepare rare-earth La-anchored WS2 / WO3 3-x Heterojunction photocatalytic material, wherein the rare earth La anchors WS2 / WO 3-x Heterojunction photocatalytic materials are used for visible light photocatalysis of N2 to NH3 at room temperature and pressure.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] 1. This invention relates to heterojunction materials WS2 / WO 3-x The modification, by adjusting the oxygen vacancy concentration through rare earth single-atom La, improved the separation ability and efficiency of photogenerated electrons and holes, and at the same time enhanced the performance of photocatalytic reduction of N2 to NH3.

[0022] 2. This invention designs and synthesizes oxygen-vacancy-rich rare earth La-anchored WS2 / WO by high-temperature hydrogen reduction. 3-x Heterojunction photocatalytic materials, due to the introduction of rare earth ions, have enhanced light absorption capacity, increased oxygen vacancy content, and enhanced built-in electric field strength. This allows photogenerated electrons and holes to be rapidly separated and migrated, thereby promoting the adsorption and activation of N2 molecules and significantly improving their photocatalytic nitrogen fixation performance.

[0023] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by means of embodiments of the invention. Attached Figure Description

[0024] Figure 1 It's La-WS2 / WO 3-x WS2 / WO 3-x WO 3-x Ammonia production of WS2 sample under full-spectrum irradiation for five hours;

[0025] Figure 2 It's La-WS2 / WO 3-x WS2 / WO 3-x WO 3-xAmmonia production per hour of WS2 sample under full-spectrum irradiation;

[0026] Figure 3 It's La-WS2 / WO 3-x Ammonia production under different conditions under full-spectrum irradiation of the sample;

[0027] Figure 4 It's La-WS2 / WO 3-x WS2 / WO 3-x WO 3-x X-ray diffraction (XRD) pattern of WS2 sample;

[0028] Figure 5 It's La-WS2 / WO 3-x WS2 / WO 3-x WO 3-x UV diffuse reflectance of WS2 sample;

[0029] Figure 6 It's La-WS2 / WO 3-x WS2 / WO 3-x WO 3-x Photocurrent response diagram of WS2 sample;

[0030] Figure 7 It's La-WS2 / WO 3-x WS2 / WO 3-x WO 3-x N2 adsorption isotherm of WS2 sample. Detailed Implementation

[0031] Embodiments of the present invention are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0032] These and other aspects of the embodiments of the present invention will become clear from the following description and accompanying drawings. In these descriptions and drawings, some specific embodiments of the present invention are specifically disclosed to illustrate some ways of implementing the principles of the embodiments of the present invention; however, it should be understood that the scope of the embodiments of the present invention is not limited thereto.

[0033] Example 1

[0034] This invention provides a rare earth La-anchored WS2 / WO 3-x Heterojunction photocatalytic material, characterized by: using WS2 / WO 3-xAs a matrix, rare earth element La is doped into its lattice, wherein La is dispersed in the form of single atoms, and the rare earth element La and WS2 / WO 3-x The mass ratio is 0.01 to 0.05:1.

[0035] Example 2

[0036] This invention provides a rare earth La-anchored WS2 / WO 3-x A method for preparing heterojunction photocatalytic materials, wherein the method is used to prepare the above-mentioned rare earth La-anchored WS2 / WO 3-x Heterojunction photocatalytic materials, wherein the method includes the following steps:

[0037] Step 1: Preparation of WS2 nanosheets by ultrasonic exfoliation:

[0038] 0.1 g of tungsten disulfide and 70 mL of N-methylpyrrolidone were added to a beaker, where N-methylpyrrolidone acted as an intercalating agent. The mixture in the beaker was sonicated for 5 hours to fully exfoliate the tungsten disulfide into thin nanosheets. The exfoliated nanosheets were centrifuged (at 7500 r / min), the product was collected, and vacuum dried to obtain dark gray WS2 nanosheets.

[0039] Step 2: In-situ hydrothermal preparation of heterojunction WS2 / WO 3-x :

[0040] First, weigh 1g of H2WO4 and 0.1g of WCl6 and add them to 30mL of anhydrous ethanol. After stirring for 10min, add 0.1g of exfoliated WS2 nanosheets and continue stirring for 20min. Then, transfer the mixture to a polytetrafluoroethylene-lined reactor and heat it at 100℃ for 24h using hydrothermal heating. After cooling to room temperature, wash it several times with anhydrous ethanol and dry it in a vacuum oven at 60℃ for 8h to obtain the powdered WS2 / WO3 precursor.

[0041] Step 3: Prepare oxygen-vacancy-rich rare-earth single-atom La-anchored oxygen-vacancy-rich WS2 / WO by high-temperature hydrogen reduction. 3-x Heterojunction photocatalytic materials:

[0042] Two g of the prepared WS2 / WO3 powder and 0.02 g of lanthanum nitrate hexahydrate were ground in a mortar for 10 min. After grinding, the powder was placed in a magnetic boat and calcined in a tube furnace at 500 °C for 3 h in an atmosphere of H2 / N2 mixed gas with a H2 content of 10% to obtain rare earth single-atom La-anchored oxygen-rich vacancy WS2 / WO3. 3-x Heterojunction photocatalyst (La-WS2 / WO) 3-x ).

[0043] Example 3

[0044] This invention provides a rare earth La-anchored WS2 / WO 3-x A method for preparing heterojunction photocatalytic materials, wherein the method is used to prepare the above-mentioned rare-earth single-atom La-anchored oxygen-rich vacancy WS2 / WO 3-x Heterojunction photocatalytic materials, wherein the method includes the following steps:

[0045] Step 1: Preparation of WS2 nanosheets by ultrasonic exfoliation:

[0046] 0.2 g of tungsten disulfide and 85 mL of N-methylpyrrolidone were added to a beaker, where N-methylpyrrolidone acted as an intercalating agent. The mixture in the beaker was sonicated for 5 h to fully exfoliate the tungsten disulfide into thin nanosheets. The exfoliated nanosheets were centrifuged (at 7500 r / min), the product was collected, and vacuum dried to obtain dark gray WS2 nanosheets.

[0047] Step 2: In-situ hydrothermal preparation of heterojunction WS2 / WO 3-x :

[0048] First, weigh 2g of H2WO4 and 0.2g of WCl6 and add them to 40mL of anhydrous ethanol. After stirring for 10min, add 0.2g of exfoliated WS2 nanosheets and continue stirring for 20min. Then, transfer the mixture to a polytetrafluoroethylene-lined reactor and heat it at 100℃ for 24h using hydrothermal heating. After cooling to room temperature, wash it several times with anhydrous ethanol and dry it in a vacuum oven at 60℃ for 8h to obtain the powdered WS2 / WO3 precursor.

[0049] Step 3: Prepare oxygen-vacancy-rich rare-earth single-atom La-anchored oxygen-vacancy-rich WS2 / WO by high-temperature hydrogen reduction. 3-x Heterojunction photocatalytic materials:

[0050] Two g of the prepared WS2 / WO3 powder and 0.1 g of lanthanum nitrate hexahydrate were ground in a mortar for 10 min. After grinding, the powder was placed in a magnetic boat and calcined in a tube furnace at 500 °C for 3 h in an atmosphere of H2 / N2 mixed gas with a H2 content of 10% to obtain rare earth single-atom La-anchored oxygen-rich vacancy WS2 / WO3. 3-x Heterojunction photocatalyst (La-WS2 / WO) 3-x ).

[0051] Example 4

[0052] This invention provides a rare earth La-anchored WS2 / WO 3-x A method for preparing heterojunction photocatalytic materials, wherein the method is used to prepare the above-mentioned rare-earth single-atom La-anchored oxygen-rich vacancy WS2 / WO 3-x Heterojunction photocatalytic materials, wherein the method includes the following steps:

[0053] Step 1: Preparation of WS2 nanosheets by ultrasonic exfoliation:

[0054] 0.3 g of tungsten disulfide and 100 mL of N-methylpyrrolidone were added to a beaker, where N-methylpyrrolidone acted as an intercalating agent. The mixture in the beaker was sonicated for 5 h to fully exfoliate the tungsten disulfide into thin nanosheets. The exfoliated nanosheets were centrifuged (at 7500 r / min), the product was collected, and vacuum dried to obtain dark gray WS2 nanosheets.

[0055] Step 2: In-situ hydrothermal preparation of heterojunction WS2 / WO 3-x :

[0056] First, weigh 3g of H2WO4 and 0.3g of WCl6 and add them to 50mL of anhydrous ethanol. After stirring for 10min, add 0.3g of exfoliated WS2 nanosheets and continue stirring for 20min. Then, transfer the mixture to a polytetrafluoroethylene-lined reactor and heat it at 100℃ for 24h using hydrothermal heating. After cooling to room temperature, wash it several times with anhydrous ethanol and dry it in a vacuum oven at 60℃ for 8h to obtain the powdered WS2 / WO3 precursor.

[0057] Step 3: Prepare oxygen-vacancy-rich rare-earth single-atom La-anchored oxygen-vacancy-rich WS2 / WO by high-temperature hydrogen reduction. 3-x Heterojunction photocatalytic materials:

[0058] Two g of the prepared WS2 / WO3 powder and 0.06 g of lanthanum nitrate hexahydrate were ground in a mortar for 10 min. After grinding, the powder was placed in a magnetic boat and calcined in a tube furnace at 500 °C for 3 h in an atmosphere of H2 / N2 mixed gas with a H2 content of 10% to obtain rare earth single-atom La-anchored oxygen-rich vacancy WS2 / WO3. 3-x Heterojunction photocatalyst (La-WS2 / WO) 3-x ).

[0059] Example 5

[0060] This invention provides a rare earth La-anchored WS2 / WO 3-x Applications of heterojunction photocatalytic materials, using the above-mentioned preparation method to prepare rare-earth La-anchored WS2 / WO3 3-x Heterojunction photocatalytic material, wherein the rare earth La anchors WS2 / WO 3-x Heterojunction photocatalytic materials are used for visible light photocatalysis of N2 to NH3 at room temperature and pressure.

[0061] To verify the effectiveness of the present invention, a simulation experiment of photocatalytic N2 reduction was conducted to evaluate its performance. The following uses the La-WS2 / WO2 prepared in Example 3 of the present invention as an example.3-x The samples were used as the evaluation objects in the experiment, and the specific process is as follows:

[0062] The ammonia content after color development was measured using a UV-Vis spectrophotometer. In short, a 300W xenon lamp was used to simulate full-spectrum sunlight, and the light intensity at the reactor location was 81.40 mW·cm². -2 The circulating condensate system is used to maintain the temperature of the reaction apparatus at a constant 15℃. 30 mg of catalyst is weighed into 80 mL of methanol solution (containing 10 mL of methanol and 70 mL of deionized water), and N2 (80 mL·min⁻¹) is continuously introduced. -1 After a 1-hour dark reaction, 3 mL of the suspension was collected. Then, the mixture was irradiated with light, and 3 mL of the suspension was collected every hour, followed by centrifugation of the supernatant. The absorbance at 655 nm was then measured using an indole blue indicator on a UV-Vis spectrophotometer. The NH3 concentration was calculated using the standard curve method.

[0063] like Figure 1 and Figure 2 The information provided indicates that after 5 hours of reaction under Xe full-spectrum irradiation, La-WS2 / WO 3-x The photocatalytic nitrogen fixation performance of this sample was significantly higher than that of other samples. The yield of NH3 reached 624.3 μmol·g within 5 hours. -1 It is WS2 / WO 3-x Sample (501.5 μmol·g) -1 1.2 times that of pure WO 3-x (129.3 μmol·g) -1 The yield of NH3 increased by 4.8 times compared to the previous year. This improvement was observed as the synthesis temperature gradually decreased. This is because higher temperatures lead to more defects, with excess oxygen vacancies becoming carrier trapping centers, resulting in reduced activity. Similarly, the average NH3 yield on the sample under full-spectrum irradiation was also observed. La-WS2 / WO 3-x The NH3 yield reached 124.9 μmol·g over the full spectrum. -1 ·h -1 Meanwhile, in order to verify the necessary conditions for the catalytic process, controlled experiments were conducted, starting from... Figure 3 It can be seen that a small amount of NH3 is produced when air enters the reaction system. Since the reactant gas N2 is replaced by Ar, no NH3 is produced in the reaction system, proving that the system generates NH3 through N2 photofixation. Furthermore, no NH3 is produced when N2 fixation is carried out without a photocatalyst or under dark conditions.

[0064] Figure 4 These are the XRD patterns of each sample. From the figures, it can be seen that WO 3-x and WS2 samples with WO 3-xThe classic diffraction peaks of WS2 (JCPDS NO. 53-0434) and WS2 (JCPDS NO. 08-0237) are in excellent agreement. Furthermore, the classic diffraction peaks of WS2 / WO are also consistent. 3-x andLa-WS2 / WO 3-x The sample contains typical diffraction planes of WS2 (002), (004), and (103), as well as WO2. 2.9 The typical diffraction planes are (010) and (020). This indicates that the heterostructure was successfully synthesized. Furthermore, no diffraction peaks of La metal clusters were observed in the diffraction pattern, indicating that they are highly dispersed La single atoms.

[0065] in addition, Figure 5 This is the UV-vis-DRS spectrum of the sample, La-WS2 / WO. 3-x The light absorption range of the sample is within WO 3-x Between WS2 and WS2, a redshift occurred, causing its band gap to narrow.

[0066] Figure 6 The photocurrent response curve of the prepared catalyst is provided. The photocurrent density-time curve represents the generation of photogenerated charges in the semiconductor photocatalyst, while a lower photocurrent density indicates a higher recombination probability between photogenerated electrons and holes. As shown in the figure, the sample La-WS2 / WO 3-x The photocurrent response is stronger, thus indicating that La-WS2 / WO 3-x It can generate more photogenerated carriers, and can more effectively separate and transfer photogenerated electrons / holes.

[0067] Meanwhile, to investigate the effect of the sample's specific surface area on catalytic activity, this embodiment conducted N2 physical adsorption-desorption tests on the sample, such as... Figure 7 As shown, WS2 / WO 3-x andLa-WS2 / WO 3-x The sample exhibits an H3 hysteresis loop within a relative pressure range of 0.4–1.0. According to the Brunauer-Deming-Deming-Teller (BDDT) model, the isotherm curve of the synthesized sample is a type IV curve, indicating that there may be slit pores formed by the accumulation of nanosheets in the sample.

[0068] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0069] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A rare earth La-anchored WS2 / WO 3-x A method for producing a heterojunction photocatalytic material, characterized by, The method comprises the following steps: Step 1, ultrasonic exfoliation preparation of WS2 nanosheet: In a beaker, add tungsten disulfide and intercalation agent to obtain a mixed solution, and perform ultrasonic operation to exfoliate the tungsten disulfide into nanosheets; centrifugal separation is performed on the mixed solution after ultrasonic operation, the product is collected, and the exfoliated nanosheets are obtained; vacuum drying is performed on the exfoliated nanosheets to obtain dark gray WS2 nanosheets; Step 2, in-situ hydrothermal method for preparing heterojunction WS2 / WO3: H2WO4 and WCl6 are added to anhydrous ethanol, stirred for c time, and then the exfoliated WS2 nanosheets are added and stirred for d time; after stirring is completed, it is transferred to a polytetrafluoroethylene-lined reaction kettle, heated at e temperature for f time, cooled to room temperature, washed with anhydrous ethanol several times, dried in a vacuum drying oven at g temperature for h time, and a powder sample WS2 / WO3 precursor is obtained; Step 3, preparation of rare earth monatomic La anchored oxygen-rich vacancy WS2 / WO by high-temperature hydrogen reduction 3-x Heterojunction photocatalytic material: The prepared WS2 / WO3 powder and lanthanum nitrate hexahydrate are put into a mortar and ground for i time, and after grinding is completed, they are put into a magnetic boat and calcined in a tube furnace under the atmosphere of a mixed gas of H2 / N2 at a temperature of j for k time to obtain a rare earth La-anchored WS2 / WO 3-x Heterojunction photocatalytic material.

2. The rare earth La-anchored WS2 / WO 3-x A method for producing a heterojunction photocatalytic material, characterized by, In the step 1, the tungsten disulfide is 0.1-0.3 g, the intercalation agent is N-methyl pyrrolidone, and the preset volume of N-methyl pyrrolidone is 70-100 mL.

3. The rare earth La-anchored WS2 / WO 3-x A method for producing a heterojunction photocatalytic material, characterized by, In the step 2, the mass of H2WO4 is 1-3 g, the mass of WCl6 is 0.1-0.3 g, the mass of WS2 nanosheet is 0.1-0.3 g, and the preset volume of anhydrous ethanol is 30-50 mL.

4. The rare earth La-anchored WS2 / WO 3-x A method for preparing a heterojunction photocatalytic material, characterized by, In the step 2, the mass ratio of WS2 to H2WO4 is 1:

10.

5. The rare earth La-anchored WS2 / WO 3-x A method for preparing a heterojunction photocatalytic material, characterized by, In the step 3, the mass of WS2 / WO3 powder is 2 g, and the mass of lanthanum nitrate hexahydrate is 0.02-0.1 g.

6. The rare earth La-anchored WS2 / WO 3-x A method for preparing a heterojunction photocatalytic material, characterized by, a time is 5 h, the centrifugal separation speed is 7500 r / min, c time is 10 min, d time is 20 min, e temperature is 100℃, f time is 24 h, g temperature is 60℃, h time is 8 h, i time is 10 min, j temperature is 500℃, and k time is 3 h.

7. The rare earth La-anchored WS2 / WO 3-x A method for preparing a heterojunction photocatalytic material, characterized by, In the step 2, the H2 content in the mixed gas of H2 / N2 is 10%.

8. A rare earth La-anchored WS2 / WO 3-x Heterojunction photocatalytic material characterized by comprising: The rare earth La-anchored WS2 / WO 3-x is prepared by the method for preparing a heterojunction photocatalytic material, and the rare earth La-anchored WS2 / WO 3-x is prepared by the method for preparing a heterojunction photocatalytic material, and the rare earth La-anchored WS2 / WO 3-x is prepared by the method for preparing a heterojunction photocatalytic material, and the rare earth La-anchored WS2 / WO 3-x is prepared by the method for preparing a heterojunction photocatalytic material, and the rare earth La-anchored WS2 / WO 9. A rare earth La-anchored WS2 / WO 3-x application of the heterojunction photocatalytic material, the rare earth La-anchored WS2 / WO 3-x The heterojunction photocatalytic material is characterized in that, The rare earth La anchors WS2 / WO 3-x Heterojunction photocatalytic materials are used for visible light photocatalytic conversion of N2 into NH3 at normal temperature and pressure.

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