Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic materials and their application in photocatalytic hydrogen production

Abstract

The present invention discloses a Cu 2‑x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere p-n type heterojunction photocatalytic materials and their photocatalytic hydrogen production applications. Using Cu2O hollow nanospheres as templates, a two-step sulfurization method was used to prepare defective biomimetic hollow Cu 2‑x S@Zn 3.74 Ga 1.02 S 5.24 (Cu 2‑x S@ZGS) p-n type heterojunction photocatalytic material. Cu 2‑x The S@ZGS p-n type heterojunction promotes the photogenerated holes to the inner Cu layer 2‑x S migrates, an oxidation reaction occurs on it, and at the same time promotes the migration of photogenerated electrons to the outer ZGS layer, where a proton reduction reaction occurs, thereby improving the spatial separation efficiency of electrons and holes. In addition, Cu 2‑x Cu defects in S further promote h + The rapid transfer of ZGS, the S defects exposed active sites enhance the hydrophilicity, and Cu 2‑ x S hollow structure and Zn 3.74 Ga 1.02 S 5.24 The thin layered structure provides a large specific surface area and more active sites, which is conducive to the adsorption of reactants and catalytic reactions, and exhibits good photocatalytic stability during the photocatalytic process.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocatalytic materials, and specifically relates to a Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic materials and their applications in photocatalytic hydrogen production. Background Art

[0002] In recent years, photocatalytic technology that converts light energy into chemical energy has become one of the effective ways to solve the energy crisis and environmental pollution problems. Among the many reported photocatalysts, bimetallic sulfides have been widely used in CC coupling reactions, CO2 reduction, photocatalytic hydrogen production, etc. due to their low cost and high conductivity. The development of high-performance bimetallic sulfide photocatalytic materials with diverse compositions, controllable structures and special morphologies remains a direction of interest and attention. II 1-x M III x (OH)2](A n- ) x / n ·mH2O), layered double hydroxides, which have large specific surface areas and tunable structures. Cu2O@ZnCr-LDH can be used for photocatalytic hydrogen production, but the hydrogen production is low. Layered double hydroxides maintain their layered structure during the conversion process, and their use as precursors offers various possibilities for preparing bimetallic sulfides with more active sites and adjustable structural and compositional diversity. For example, Duan et al. prepared CoNi-LDH on nickel foam, then used hydrogen reduction calcination and partial sulfurization to obtain CoNi alloy@(Co,Ni)9S8 materials. Yu et al. hydrothermally sulfurized the synthesized CoFe-LDH / GO to obtain nanosheet-shaped bimetallic CoFeS2 / GO materials. These materials are used in capacitors, batteries, electrocatalysis, photocatalysis, and other applications, but their use as photocatalysts has been rarely reported, possibly due to their wide band gaps, easy electron-hole recombination, susceptibility to photocorrosion, and poor activity.

[0003] Common methods for improving the performance of photocatalytic reactions mainly include heterostructure construction, element doping, precious metal loading, defect construction, and morphology control. Among them, constructing a reasonable heterojunction (Z-type heterojunction, S-type heterojunction, pn-type heterojunction, type-II heterojunction, etc.) is one of the most effective means to promote rapid carrier separation. On the other hand, the photocatalytic reaction occurring on semiconductors requires that the photooxidation and photoreduction sites must be strictly separated in the nanospace, which not only inhibits the recombination of carriers migrating to the surface, but also promotes the efficiency of surface reactions. Therefore, there is an urgent need to develop methods that can simultaneously promote the rapid migration of holes and electrons, achieve spatial charge separation of photogenerated carriers, and inhibit their recombination.

[0004] Selecting a p-type co-catalyst with energy band matching and an n-type bimetallic sulfide composite to construct a pn-type heterojunction can achieve high-efficiency photocatalytic reaction performance. 2-x Sulfur, a defective p-type sulfide semiconductor, can effectively extract photogenerated holes as a hole cocatalyst, making it a suitable material for constructing pn-type heterojunctions. Inspired by the hollow vesicle structure of plant photosynthetic thylakoids, whose spatially separated cavity and matrix serve as the H2O oxidation center (photosystem II) and CO2 reduction center (photosystem I) in photosynthesis, biomimetic hollow heterojunction composite photocatalysts have been prepared. These composites not only reflect and scatter light within the cavity, enhancing light absorption and mass transfer, but also provide spatially separated sites for redox reactions, effectively separating electrons and holes. For example, Lou et al. used In-MIL-68 as a precursor to prepare a "sandwich structure" of In2O3@ZnIn2S4 hollow hexagonal prism photocatalyst for efficient photocatalytic CO2 reduction. Furthermore, a Co9S8@ZnIn2S4 heterojunction was constructed by coating 2D ZnIn2S4 nanosheets on a Co9S8 hollow cage structure, improving photocatalytic hydrogen production performance. This encapsulation structure improves the stability of the inner layer by improving the chemical resistance of the outer layer. Summary of the Invention

[0005] The purpose of the present invention is to provide a pn-type heterojunction photocatalytic material that can quickly transfer holes and effectively separate electrons and holes at spatial sites, that is, to form a pn-type heterojunction photocatalytic material on Cu by two-step sulfurization. 2-x Growth of Zn on the surface of S hollow nanospheres 3.74 Ga 1.02 S 5.24 nanosheets, constructed of Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic materials.

[0006] For the above purpose, the Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 The hollow nanosphere pn-type heterojunction photocatalytic material is prepared by the following method:

[0007] Step 1: Spherical Cu2O is dispersed in deionized water, and sodium sulfide is added and stirred at room temperature. The resulting black suspension is transferred to an autoclave and aged at 180-220°C for 4-12 hours. After cooling to room temperature, the reaction product is washed with deionized water and anhydrous ethanol, and vacuum dried to obtain Cu2S hollow nanospheres. The mass ratio of the spherical Cu2O to sodium sulfide is 1:4-10.

[0008] Step 2: Dispersing the Cu2S hollow nanospheres into a mixed solution of deionized water and anhydrous ethanol, then adding zinc nitrate, gallium nitrate, and sodium borate, stirring evenly at room temperature, and stirring and reacting at 60-90°C for 6-12 hours. The reaction product is centrifuged and washed with deionized water and anhydrous ethanol, vacuum dried, and ground to obtain a Cu2S@ZnGa-BLDH precursor; wherein the molar ratio of the zinc nitrate, gallium nitrate, and sodium borate is 1-3:0.6-3:1-5;

[0009] Step 3: Place the Cu2S@ZnGa-BLDH precursor and elemental sulfur in a tube furnace at a mass ratio of 1:0.5-10, calcine at 300-500°C for 1-3 hours under argon atmosphere, and cool to room temperature to obtain Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, in which Cu 2-x S is Cu 1.8S and Cu 1.96 S, the mass content of the Cu2S hollow nanospheres in the photocatalytic material is 3% to 10%, preferably the mass content of the Cu2S hollow nanospheres in the photocatalytic material is 7%.

[0010] In the above step 1, the mass ratio of the spherical Cu2O to sodium sulfide is preferably 1:4.5-6.

[0011] In the above step 1, aging is preferably performed at 220° C. for 6 hours.

[0012] In the above step 2, the molar ratio of zinc nitrate, gallium nitrate and sodium borate is preferably 3:1:3.

[0013] In the above step 2, the reaction is preferably carried out at 70 to 80° C. for 10 to 12 hours.

[0014] In the above step 3, the mass ratio of the Cu2S@ZnGa-BLDH precursor to the sublimed sulfur is preferably 1:2-4.

[0015] In the above step 3, the calcination is preferably carried out at 400-500° C. for 2 hours under an argon atmosphere.

[0016] In the above step 3, the heating rate of the calcination is preferably 1 to 3°C / min.

[0017] Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic materials can be used for photocatalytic hydrogen production.

[0018] The beneficial effects of the present invention are as follows:

[0019] The present invention uses Cu2O hollow nanospheres as templates and adopts a two-step sulfurization method to prepare defective bionic hollow Cu 2- x S@Zn 3.74 Ga 1.02 S 5.24 pn-type heterojunction photocatalytic materials. The biomimetic hollow structure not only causes light to be reflected and scattered in the cavity to enhance light absorption and improve mass transfer, but also provides spatially separated sites for redox reactions. 2-x S and n-type Zn with S defects 3.74 Ga 1.02 S 5.24 The pn junction formed between Zn 3.74 Ga 1.02 S 5.24 The photogenerated holes move to Cu 2-x S migration and Cu 2-x The photogenerated electrons of S to Zn 3.74 Ga 1.02 S 5.24 The promotion of migration and the spatial separation of redox sites effectively improve its photocatalytic hydrogen production performance. 2-x Cu defects in S further promote h + Rapid transfer of Zn 3.74 Ga 1.02 S 5.24 The S defects in Cu expose active sites and enhance hydrophilicity. 2-x S hollow structure and Zn 3.74 Ga 1.02 S 5.24 The thin layer structure provides a large specific surface area and more active sites, which is conducive to the adsorption of reactants and the occurrence of catalytic reactions, and shows good photocatalytic stability in the photocatalytic process. 2-x The photocatalytic hydrogen production of S@ZGS (269 μmol g -1 h -1 ) are pure phase Cu 2-x 44 and 3 times that of S and ZGS; 7% Cu under visible light 2-x The photocatalytic hydrogen production of S@ZGS (180 μmol g -1 h -1 ) are pure phase Cu2S, Cu 2-x 36, 30 and 25 times of S and ZGS. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 is a SEM image of the Cu2S hollow nanospheres prepared in Example 1.

[0021] Figure 2 This is the XRD pattern of the Cu2S@ZnGa-BLDH precursor prepared in Example 1.

[0022] Figure 3 These are the SEM (b) and TEM (c) images of the Cu2S@ZnGa-BLDH precursor prepared in Example 1.

[0023] Figure 4 This is the TG-DSC curve of the Cu2S@ZnGa-BLDH precursor prepared in Example 1.

[0024] Figure 5 It is Cu 2-x S, Zn 3.74 Ga 1.02 S 5.34 (ZGC), Cu 2-x S@Zn 3.74 Ga 1.02 S 5.34 (7% Cu 2-x XRD pattern of S@ZGC).

[0025] Figure 6 The Cu prepared in Example 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 SEM (a), TEM (b), HRTEM (c) and mapping (d) images.

[0026] Figure 7 Cu2S, Cu 2-x S, Zn 3.74 Ga 1.02 S 5.24 (ZGC), Cu2S@ZnGa-BLDH (7% Cu2S@ZnGa-BLDH) prepared in Example 1 and Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 (7%Cu 2-x S@ZGC), Cu prepared in Example 2 2-x S@Zn 3.74 Ga 1.02 S 5.24 (3%Cu 2-x S@ZGC), and Cu prepared in Example 3 2-x S@Zn 3.74 Ga 1.02 S 5.24 (10% Cu 2-xPhotocatalytic hydrogen production curve of S@ZGC) under visible light irradiation.

[0027] Figure 8 The Cu prepared at different temperatures in Example 1, Example 4 and Example 5 is 2-x S@Zn 3.74 Ga 1.02 S 5.24 (7%Cu 2-x Photocatalytic hydrogen production curve of S@ZGC) under visible light irradiation. DETAILED DESCRIPTION

[0028] The present invention will be further described in detail below with reference to the accompanying drawings and examples, but the protection scope of the present invention is not limited to these examples.

[0029] Example 1

[0030] Step 1: Take 50mg of spherical Cu2O and disperse it in 50mL of deionized water, add 0.24g of Na2S·9H2O, stir at room temperature for 30 minutes, transfer the resulting black suspension to a high-pressure reactor, and age it at 220℃ for 6 hours; after cooling to room temperature, wash it with deionized water and anhydrous ethanol several times, and dry it in a vacuum drying oven at 60℃ for 12 hours to obtain black Cu2S hollow nanospheres. Figure 1 It can be seen that Cu2O can be hydrothermally sulfided to obtain rough surface hollow spheres Cu2S in one step, and the shell thickness is about 63nm. This may be because S 2- In addition to reacting with the surface of Cu2O spheres, S 2- At high temperatures, it is also easy to corrode the (111) crystal plane with higher surface energy of Cu2O and enter the material from there to etch the internal Cu2O.

[0031] Step 2: Take 20 mg of Cu2S hollow nanospheres and ultrasonically disperse them in a mixed solution of 50 mL of deionized water and anhydrous ethanol with a volume ratio of 4:1, add 0.891 g (3 mmol) Zn(NO3)2·6H2O, 0.255 g (1 mmol) Ga(NO3)3·4H2O, and 1.144 g (3 mmol) Na2B4O7·4H2O, stir at room temperature for 30 minutes, and then stir and react at 80°C for 12 hours; after cooling to room temperature, the reaction product is washed several times with deionized water and anhydrous ethanol, placed in a vacuum drying oven at 60°C for 12 hours, and then ground to obtain the Cu2S@ZnGa-BLDH precursor.

[0032] Figure 2 、 Figure 3 XRD, SEM and TEM images of Cu2S@ZnGa-BLDH precursor. Figure 2The XRD pattern shows that there are both Cu2S and LDH diffraction peaks, among which 46.2° is the (110) crystal plane of Cu2S, while the characteristic peaks at 9.8°, 19.9°, 33.8°, 37.3°, 43.2° and 60.3° correspond to the (003), (006), (012), (015) and (110) crystal planes of LDH. According to Bragg's law, the borate-intercalated LDH has a large interlayer spacing (d 003 =0.896nm) with ultrathin nanosheets, from Figure 3 It can be seen from the SEM and TEM images that the surface of the Cu2S hollow nanospheres is uniformly wrapped by the in situ grown ZnGa-BLDH ultrathin nanosheets. Figure 4 The TG-DSC curve of Cu2S@ZnGa-BLDH shows three stages of weight loss: the first stage, from room temperature to 340°C, shows a 17.9% weight loss. The DSC curve shows an endothermic peak at 256°C, likely due to the removal of surface water and crystalline water. The second stage, from 340°C to 570°C, shows a weight loss of approximately 2.8%, with an exothermic peak at 364°C, attributed to the dehydroxylation of the ZnGa-BLDH layers and the dehydration of interlayer borate anions to form amorphous B2O3. The third stage, from 570°C to 800°C, shows a 2.4% weight loss, likely due to the partial oxidation of Cu2S by lattice oxygen.

[0033] Step 3: Take the Cu2S@ZnGa-BLDH precursor and elemental sulfur in a mass ratio of 1:2 and place them in a tube furnace. In an argon atmosphere, heat the mixture to 500°C at a rate of 2°C / min, calcine at a constant temperature for 2 hours, and cool to room temperature to obtain Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn type heterojunction photocatalytic material, Cu in the obtained photocatalytic material 2-x The mass content of S is 7%.

[0034] Depend on Figure 5 Cu 2-x S, Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 、Zn 3.74 Ga 1.02 S 5.24 From the XRD pattern of Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 The peak positions correspond to the cubic Cu 1.8 S (JCPDS No.24-0061) and square Cu1.92 Cu composed of S (JCPDS No.29-0578) 2-x S, and hexagonal Zn 3.74 Ga 1.02 S 5.24 The diffraction peaks of (JCPDS No.49-1627) indicate that the two semiconductors are successfully constructed into a heterojunction. Figure 6 Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 From the SEM and TEM images, it can be seen that the hollow core-shell structure has basically no obvious changes, while from the HRTEM image, the lattice fringes of 0.39 and 0.29 nm correspond to Cu 2-x The (110) crystal plane of S and Zn 3.74 Ga 1.02 S 5.24 The (100) crystal plane of Cu is fuzzy, indicating that the heterojunction is formed by close contact. 2-x S and Zn 3.74 Ga 1.02 S 5.24 The inner circle shows that the lattice points are discontinuous, indicating that there are defects. The mapping diagram shows the distribution of Zn, Ga, Cu, and S elements. It can be seen that Cu and S elements are mainly distributed on the outline of the hollow sphere, while Zn, Ga and a small amount of S elements are distributed outside the outline, indicating that Zn 3.74 Ga 1.02 S 5.24 Successfully wrapped in Cu 2-x Cu formed on the S surface 2-x S@Zn 3.74 Ga 1.02 S 5.24 Heterojunction.

[0035] Example 2

[0036] In step 2 of this embodiment, the amount of Cu2S hollow nanospheres was reduced from 20 mg to 10 mg, and the other steps were the same as in embodiment 1 to obtain Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn type heterojunction photocatalytic material, Cu in the obtained photocatalytic material 2-x The mass content of S is 3%.

[0037] Example 3

[0038] In step 2 of this embodiment, the amount of Cu2S hollow nanospheres was increased from 20 mg to 30 mg, and the other steps were the same as in Example 1 to obtain Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn type heterojunction photocatalytic material, Cu in the obtained photocatalytic material 2-x The mass content of S is 10%.

[0039] Example 4

[0040] The Cu2S@ZnGa-BLDH sample was calcined in a tube furnace with Ar flow at 300°C for 2h at a heating rate of 2°C / min. The other steps were the same as in Example 1 to obtain Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic materials.

[0041] Example 5

[0042] The Cu2S@ZnGa-BLDH sample was calcined in a tube furnace with Ar flow at 400℃ for 2h at a heating rate of 2℃ / min to obtain Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic materials.

[0043] Example 6

[0044] Cu prepared in Examples 1 to 5 2-x S@Zn 3.74 Ga 1.02 S 5.24 Application of hollow nanosphere pn-type heterojunction photocatalytic materials for photocatalytic hydrogen production

[0045] Take 10mg of photocatalytic material and disperse it in 5mL of mixed aqueous solution containing 0.35M Na2S and 0.25M Na2SO3. Then, purify the air in the reactor by passing argon gas for 20 minutes under magnetic stirring. Then, irradiate the reactor under a 300W xenon lamp with a 420nm cutoff for 5 hours. Collect and detect the gas generated in the reactor every hour. 2-x S, Zn 3.74 Ga 1.02 S 5.24 , Cu2S@ZnGa-BLDH for comparative experiments.

[0046] Figure 6 Cu2S, Zn3.74 Ga 1.02 S 5.24 、Cu2S@ZnGa-BLDH、Cu 2-x S and different Cu prepared in Examples 1 to 3 2- x S mass content of Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Photocatalytic performance of photocatalyst for water decomposition and hydrogen production under visible light. 2-x S produces almost no hydrogen in simulated sunlight and visible light, Zn 3.74 Ga 1.02 S 5.24 The photocatalytic hydrogen production rate was 80 and 7 μmol g under simulated sunlight and visible light, respectively. -1 h -1 ), the photocatalytic performance of the heterojunction formed by the two is significantly improved. 2-x S mass content of 7% Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 The photocatalytic hydrogen production under simulated sunlight (269 μmol g -1 h -1 ) are Cu 2-x S and Zn 3.74 Ga 1.02 S 5.24 The photocatalytic hydrogen production under visible light (180 μmol g -1 h -1 ) are pure phase Cu2S, Cu 2-x S and Zn 3.74 Ga 1.02 S 5.24 36, 30 and 25 times of Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 The hydrogen production performance of Cu 2-x S and Zn 3.74 Ga 1.02 S 5.24 Content is related to Cu 2-x The optimal mass content of S is 7%, and its hydrogen production is three times that of the unsulfurized Cu2S@ZnGa-BLDH precursor.

[0047] Figure 7 Cu obtained by sulfurization at different temperatures in Example 1, Example 4 and Example 5 2-x S@Zn3.74 Ga 1.02 S 5.34 The photocatalytic hydrogen production performance under visible light. It can be seen from the figure that with the increase of sulfurization temperature, the hydrogen production effect gradually increases, which is related to the increase in sample crystallinity.

Claims

1. A Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized in that: The photocatalytic material is prepared by the following method: Step 1: Spherical Cu2O is dispersed in deionized water, and sodium sulfide is added and stirred at room temperature. The resulting black suspension is transferred to an autoclave and aged at 180-220°C for 4-12 hours. After cooling to room temperature, the reaction product is washed with deionized water and anhydrous ethanol, and vacuum dried to obtain Cu2S hollow nanospheres. The mass ratio of the spherical Cu2O to sodium sulfide is 1:4-10. Step 2: Dispersing the Cu2S hollow nanospheres into a mixed solution of deionized water and anhydrous ethanol, then adding zinc nitrate, gallium nitrate, and sodium borate, stirring evenly at room temperature, and stirring and reacting at 60-90°C for 6-12 hours. The reaction product is centrifuged and washed with deionized water and anhydrous ethanol, vacuum dried, and ground to obtain a Cu2S@ZnGa-BLDH precursor; wherein the molar ratio of the zinc nitrate, gallium nitrate, and sodium borate is 1-3:0.6-3:1-5; Step 3: Place the Cu2S@ZnGa-BLDH precursor and elemental sulfur in a tube furnace at a mass ratio of 1:0.5-10, calcine at 300-500°C for 1-3 hours under argon atmosphere, and cool to room temperature to obtain Cu 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, in which Cu 2-x S is Cu 1.8S and Cu 1.96 S, the mass content of Cu2S hollow nanospheres in the photocatalytic material is 3% to 10%.

2. Cu according to claim 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized by: In step 1, the mass ratio of the spherical Cu2O to sodium sulfide is 1:4.5-6.

3. Cu according to claim 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized by: In step 1, aging is performed at 220° C. for 6 hours.

4. Cu according to claim 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized by: In step 2, the molar ratio of zinc nitrate, gallium nitrate and sodium borate is 3:1:

3.

5. Cu according to claim 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized by: In step 2, the reaction is carried out at 70 to 80° C. for 10 to 12 hours.

6. Cu according to claim 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized by: In step 3, the mass ratio of the Cu2S@ZnGa-BLDH precursor to sublimated sulfur is 1:2-4.

7. Cu according to claim 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized by: In step 3, the product is calcined at 400-500° C. for 2 hours under an argon atmosphere.

8. The Cu according to claim 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized by: In step 3, the heating rate of the calcination is 1-3°C / min.

9. The Cu according to claim 1 2-x S@Zn 3.74 Ga 1.02 S 5.24 Hollow nanosphere pn-type heterojunction photocatalytic material, characterized by: The mass content of the Cu2S hollow nanospheres in the photocatalytic material is 7%.

10. The Cu according to any one of claims 1 to 9 2-x S@Zn 3.74 Ga 1.02 S 5.24 Application of hollow nanosphere pn-type heterojunction photocatalytic material in photocatalytic hydrogen production.

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