Ultrasonic-assisted photodeposition of supported heterojunctions and methods of making and using the same

Abstract

This invention discloses a heterojunction of an ultrasound-assisted photodeposition supported cocatalyst, its preparation method, and its application. The method includes adding a ZnIn2S4 / metal sulfide heterojunction and triethanolamine to water, mixing them thoroughly to obtain solution A; adding a platinum source solution dropwise to solution A to obtain solution B, removing dissolved oxygen from solution B; placing solution B in an ultrasonic environment and simultaneously irradiating it with visible light; after the reaction is complete, collecting the product, which is the ultrasound-assisted photodeposition supported cocatalyst heterojunction. The cocatalyst formed by ultrasound-assisted photodeposition of this invention reduces the actual loading of the cocatalyst, thereby reducing the overall production cost. Simultaneously, the strong interfacial Pt-S bond bonding improves the stability of the cocatalyst during the reaction process, preventing aggregation and detachment, and enabling the catalytic system to maintain high efficiency for a long time.

Description

Technical Field

[0001] This invention relates to the preparation and application of photocatalysis, and more particularly to a heterojunction of an ultrasonically assisted photodeposition supported cocatalyst, its preparation method and application, belonging to the field of photocatalysis. Background Technology

[0002] Photocatalysis, which converts solar energy into hydrogen, is an ideal pathway for producing renewable fuels. Among numerous semiconductor catalysts, the two-dimensional ternary sulfide ZnIn2S4 exhibits excellent visible light absorption and a large specific surface area due to its narrow band gap and unique layered structure. However, its severe photogenerated electron-hole recombination and inefficient charge transfer significantly limit its photocatalytic hydrogen evolution performance.

[0003] To address the issue of carrier recombination, constructing heterojunctions is a commonly used strategy. While heterojunctions can significantly promote charge separation, traditional fabrication processes often introduce numerous uncontrollable defects (i.e., interface traps) at the interface. These traps easily become nonradiative recombination centers for photogenerated carriers, thereby eroding overall catalytic activity. Therefore, how to "turn waste into treasure" and transform these originally harmful interface defects into beneficial sites for improving catalytic performance is a major challenge currently faced.

[0004] Furthermore, the slow hydrogen evolution reaction (HER) kinetics on semiconductor surfaces is another major bottleneck limiting hydrogen production efficiency. Platinum (Pt) is considered a state-of-the-art cocatalyst due to its near-perfect hydrogen binding energy. However, in practical applications, high Pt loading is often required to prevent Pt particle aggregation or detachment and maintain long-term stability. This makes its high cost a significant obstacle to large-scale application. Although single-atom Pt has attracted much attention in recent years due to its extremely high atom utilization, this highly dispersed configuration is prone to migration and aggregation during catalytic reactions, leading to catalyst deactivation.

[0005] In summary, there is an urgent need to develop a new strategy that not only maximizes the atomic utilization of precious metals (such as Pt) and reduces application costs, but also effectively modulates heterojunction interface defects, utilizing these defect sites to further promote charge separation and accelerate interfacial reaction kinetics. Summary of the Invention

[0006] Objectives of the Invention: The first objective of this invention is to provide a method for preparing heterojunctions with tunable interface defects using ultrasound-assisted photodeposition; the second objective of this invention is to provide a heterojunction that can tunable interface defects, improve interface charge separation efficiency, and accelerate surface hydrogen evolution reaction; the third objective of this invention is to provide applications of the above-mentioned heterojunction.

[0007] To achieve the aforementioned primary objective, the technical solution for the heterojunction preparation method provided by this invention is as follows:

[0008] This invention provides a method for preparing a heterojunction with a supported cocatalyst via ultrasound-assisted photodeposition, comprising the following steps:

[0009] ZnIn2S4 / metal sulfide heterojunction and triethanolamine were added to water and mixed thoroughly to obtain solution A;

[0010] A platinum source solution is added dropwise to solution A to obtain solution B, and the dissolved oxygen in solution B is removed.

[0011] Solution B was placed in an ultrasonic environment and simultaneously irradiated with visible light. After the reaction was completed, the product was collected, which is the heterojunction of the ultrasonic-assisted photodeposition supported catalyst.

[0012] Preferably, the ZnIn2S4 / metal sulfide heterojunction is selected from: ZnIn2S4 / ZnS, ZnIn2S4 / CdS, ZnIn2S4 / MoS2, and ZnIn2S4 / In2S3.

[0013] Preferably, in the heterojunction with ultrasonic-assisted photodeposition of the supported cocatalyst, the platinum loading accounts for 0.024-0.545% of the total mass of the heterojunction. For example, 0.024%, 0.084%, 0.22%, 0.341%, and 0.545%. More preferably, it is 0.084-0.22%.

[0014] As a preferred option, the platinum source is selected from: chloroplatinic acid hexahydrate, tetraammineplatinum nitrate, tetraammineplatinum chloride, potassium chloroplatinate, and sodium chloroplatinate.

[0015] Preferably, solution B is purified by argon gas to remove dissolved oxygen from solution B.

[0016] Preferably, solution B is placed in an ultrasonic environment with an ultrasonic intensity of 90-360 W and an ultrasonic time of 10-50 min. More preferably, the ultrasonic intensity is 180-270 W and the ultrasonic time is 20-40 min.

[0017] Preferably, during visible light irradiation, the wavelength of the visible light is greater than 420 nm, and the irradiation time is 20-40 min. More preferably, the wavelength of the visible light is 420-780 nm.

[0018] To achieve the second objective mentioned above, the technical solution for heterojunctions provided by the present invention is as follows:

[0019] This invention provides a heterojunction for supporting a cocatalyst via ultrasound-assisted photodeposition. The heterojunction is prepared by the following method: adding a ZnIn2S4 / metal sulfide heterojunction and triethanolamine to water and mixing them thoroughly to obtain solution A; adding a platinum source solution dropwise to solution A to obtain solution B, and removing dissolved oxygen from solution B; placing solution B in an ultrasound environment and simultaneously irradiating it with visible light; after the reaction is complete, collecting the product, which is the heterojunction for supporting a cocatalyst via ultrasound-assisted photodeposition.

[0020] To achieve the aforementioned third objective, the technical solution for heterojunction applications provided by this invention is as follows:

[0021] The heterojunction provided by this invention can be used in the preparation of photocatalysts for hydrogen production.

[0022] Specifically, the method for producing hydrogen using a heterojunction as a photocatalyst includes the following steps: the heterojunction provided by the present invention is made into a photocatalyst suspension and dispersed in a 50 mL aqueous solution containing 10 vol% TEOA, wherein TEOA acts as a sacrificial electron donor, and hydrogen is produced by reaction under visible light irradiation of a 300 W xenon lamp.

[0023] Invention Principle: This invention discloses an interface defect programming and anchoring strategy based on the synergistic effect of ultrasound-assisted photodeposition. By using ultrasound, sulfur defects at the interface are specifically amplified and activated, transforming them into highly active electron-rich centers. Combined with the photodeposition process, the directional trapping effect of defects on photogenerated electrons guides the precise in-situ photoreduction of the Pt precursor at the defect sites. This synergistic strategy successfully transforms interface sulfur defects into chemically specific docking sites for Pt-S coordination. This not only achieves high dispersion and stable deployment of Pt at an ultra-low loading of 0.084 wt%, but the defect-anchored Pt-S coordination structure can also efficiently extract interface electrons and optimize hydrogen adsorption thermodynamics, significantly improving HER kinetic performance.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The preparation method is simple. A heterojunction is formed by a one-step hydrothermal method, which solves the problem of carrier recombination in the bulk phase of the photocatalyst. At the same time, potential defects and active sites are formed at the interface, avoiding the multi-step processing and complex control in the traditional method, making the preparation process simple.

[0025] (2) The cocatalyst formed by ultrasonic-assisted photodeposition reduces the actual loading of the cocatalyst, thereby reducing the overall production cost. At the same time, the strong interfacial Pt-S bond improves the stability of the cocatalyst during the reaction process, avoids agglomeration and shedding, and enables the catalytic system to maintain high efficiency for a long time.

[0026] (3) Pt loaded with defects at the heterojunction interface acts as a highly efficient co-catalyst, promoting the transfer of photogenerated electrons, reducing the surface overpotential, and accelerating the surface HER kinetics. Its excellent catalytic ability greatly improves the hydrogen evolution yield and stability of the final photocatalyst. Attached Figure Description

[0027] Figure 1 The images shown are SEM images of the photocatalysts in Example 1 and Comparative Example 1, where a is a SEM image of ZnIn2S4, b is a TEM image of ZnIn2S4, c is a SEM image of ZnIn2S4 / ZnS, d is a TEM image of ZnIn2S4 / ZnS, e is a SEM image of ZnIn2S4 / ZnS-UPt, and f is a TEM image of ZnIn2S4 / ZnS-UPt.

[0028] Figure 2 The graphs show the hydrogen production performance of ZnIn2S4, ZnIn2S4 / ZnS, and ZnIn2S4 / ZnS-UPt in Example 1 and Comparative Example 1, where ZIS represents ZnIn2S4 and ZnS represents ZS.

[0029] Figure 3 The graph shows a comparison of the hydrogen production performance of ZnIn2S4 / ZnS-UPt prepared in Example 1 with ZnIn2S4 / ZnS-U and ZnIn2S4 / ZnS-Pt in Comparative Example 2, where ZIS represents ZnIn2S4 and ZnS represents ZS.

[0030] Figure 4 The graphs show the hydrogen production performance of the catalysts in Example 2. Graph a is a line graph showing the hydrogen production performance after ultrasonic-assisted photodeposition of different volumes of H2PtCl6·6H2O solution; graph b is a graph showing the hydrogen production performance of the photocatalyst ZnIn2S4 / ZnS-UPt obtained by ultrasonic-assisted photodeposition of co-catalysts with 0, 10, 20, 30, and 60 μL of H2PtCl6·6H2O, respectively; and graph c is a graph showing the hydrogen production performance of the photocatalyst ZnIn2S4 / ZnS-UPt obtained by ultrasonic-assisted photodeposition of co-catalysts with 80, 100, 130, and 200 μL of H2PtCl6·6H2O, respectively.

[0031] Figure 5 The Pt mass percentage (ICP) of the ZnIn2S4 / ZnS-UPt photocatalyst prepared by ultrasonic-assisted photodeposition under different amounts of H2PtCl6·6H2O added (10, 30, 80, 130 and 200 μL) in Example 2 is given.

[0032] Figure 6The graphs show the hydrogen production performance of the photocatalyst in Example 3, where a represents the hydrogen production performance of ZnIn2S4 / ZnS-UPt after loading Pt at different ultrasonic durations, b represents the hydrogen production performance of ZnIn2S4 / ZnS-UPt after loading Pt at different ultrasonic intensities, and c represents the performance trend graphs for different ultrasonic durations and intensities.

[0033] Figure 7 The image shown is the XRD pattern in Example 4, where a is ZnIn2S4 / CdS, b is ZnIn2S4 / MoS2, c is ZnIn2S4 / In2S3, and Z1S is ZnIn2S4.

[0034] Figure 8 The hydrogen production performance of the photocatalysts in Example 4, Comparative Example 3, and Comparative Example 4 is shown, where a represents the hydrogen production performance of ZnIn2S4 / In2S3, ZnIn2S4 / In2S3-Pt, and ZnIn2S4 / In2S3-UPt, b represents the hydrogen production performance of ZnIn2S4 / CdS, ZnIn2S4 / CdS-Pt, and ZnIn2S4 / CdS-UPt, c represents the hydrogen production performance of ZnIn2S4 / MoS2, ZnIn2S4 / MoS2-Pt, and ZnIn2S4 / MoS2-UPt, and ZIS represents ZnIn2S4. Detailed Implementation

[0035] The technical solution of the present invention will be further described below with reference to the accompanying drawings.

[0036] Example 1

[0037] This embodiment provides a ZnIn2S4 / ZnS-UPt photocatalyst, the preparation steps of which are as follows:

[0038] 0.57512 g of zinc sulfate hydrate (ZnSO4·7H2O) and 0.58648 g of indium trichloride hydrate (InCl3·4H2O) were dissolved in 30 mL of deionized water and 20 mL of glycerol, and the mixture was stirred for 30 min. Then, 0.7513 g of thioacetamide (TAA) was added to the above solution and stirred for 90 min. The clarified precursor liquid was then placed in a 100 mL polytetrafluoroethylene liner, sealed, and heated to 170 °C for 12 h. ZnIn2S4 / ZnS nanoflowers were constructed, washed twice with deionized water and ethanol, and then freeze-dried. ZnIn2S4 / ZnS with spherical nanoflower morphology was obtained. The morphology of the ZnIn2S4 / ZnS heterostructure is shown in the figure. Figure 1As shown in c and d, ZnIn2S4 / ZnS can be seen to be spherical nanoflowers with a diameter of approximately 4 μm. Subsequently, 20 mg of ZnIn2S4 / ZnS water splitting photocatalyst powder was added to 5 mL of triethanolamine (TEOA) and 45 mL of deionized water, and the mixture was stirred for 10 min (designated as solution A). Then, 30 μL of chloroplatinic acid hydrate solution (H2PtCl6·6H2O, concentration 1.5 mg / mL) was pipetted into the solution. -1 Solution A was added dropwise to obtain solution B. Solution B was then purified with argon gas for 30 min to completely remove dissolved oxygen and establish anaerobic conditions. Synchronous ultrasound and visible light irradiation were then applied to promote platinum deposition. At room temperature, the ultrasound probe was positioned 2 cm below the surface of the suspension, and the ultrasound intensity was 180 W. Synchronous visible light irradiation (λ > 420 nm, xenon lamp source) was applied throughout the ultrasound treatment. After 30 min of ultrasound and light treatment, the sample was centrifuged and washed twice with deionized water and ethanol, then freeze-dried.

[0039] The morphology of the ZnIn2S4 / ZnS-UPt photocatalyst is as follows: Figure 1 As shown in e and f, it can be seen that ZnIn2S4 / ZnS-UPt is a spherical nanoflower with a diameter of about 4 μm, on which a 4 nm Pt single-atom ensemble catalyst is supported.

[0040] Hydrogen evolution performance testing: Hydrogen production experiments were conducted under vacuum conditions using a trace gas reaction evaluation system. A photocatalyst suspension consisting of 20 mg of catalyst was dispersed in a 50 mL aqueous solution containing 10 vol% TEOA as a sacrificial electron donor. The reaction mixture was irradiated with a 300 W xenon lamp equipped with a 420 nm cutoff filter, while a circulating cooling water system maintained the temperature at 5 °C. The reaction was carried out at a flow rate of 15 mL / min. -1 Under these conditions, hydrogen was quantified using a gas chromatograph equipped with a thermal conductivity detector (TCD), a 5Å molecular sieve packed column, and ultra-high purity argon as the carrier gas, with analysis performed every half hour.

[0041] from Figure 2 It can be seen that the photocatalyst prepared by the method in this embodiment can achieve a hydrogen evolution performance of 22.43 mmol g. -1 h -1 .

[0042] Comparative Example 1

[0043] This comparative example provides a ZnIn2S4 and ZnIn2S4 / ZnS photocatalyst.

[0044] The preparation steps for ZnIn2S4 are as follows:

[0045] 0.28756 g of zinc sulfate hydrate (ZnSO4·7H2O) and 0.58648 g of indium trichloride hydrate (InCl3·4H2O) were dissolved in 30 mL of deionized water and 20 mL of glycerol, and the mixture was stirred for 30 min. Then, 0.30752 g of thioacetamide (TAA) was added to the above solution and stirred for 90 min. The clarified precursor liquid was then placed in a 100 mL polytetrafluoroethylene liner, sealed, and heated to 170 °C for 12 h. ZnIn2S4 nanoflowers were constructed and washed twice with deionized water and ethanol, and then freeze-dried. The morphology of ZnIn2S4 is as follows. Figure 1 As shown in a and b in the figure.

[0046] The preparation steps for ZnIn2S4 / ZnS are as follows:

[0047] 0.57512 g of zinc sulfate hydrate (ZnSO4·7H2O) and 0.58648 g of indium trichloride hydrate (InCl3·4H2O) were dissolved in 30 mL of deionized water and 20 mL of glycerol, and the mixture was stirred for 30 min. Then, 0.7513 g of thioacetamide (TAA) was added to the above solution and stirred for 90 min. The clarified precursor liquid was then placed in a 100 mL polytetrafluoroethylene liner, sealed, and heated to 170 °C for 12 h. ZnIn2S4 / ZnS nanoflowers were constructed, washed twice with deionized water and ethanol, and then freeze-dried. The morphology of the ZnIn2S4 / ZnS heterojunction is shown in the figure. Figure 1 As shown in c and d.

[0048] The hydrogen evolution performance of ZnIn2S4 and ZnIn2S4 / ZnS was tested in the same manner as in Example 1, and the results are shown in [Figure 1]. Figure 2 .

[0049] from Figure 2 It can be seen that the hydrogen evolution performance of the ZnIn2S4 / ZnS photocatalyst prepared in this comparative example can reach 2.31 mmol g. -1 h -1 The hydrogen evolution property of pure-phase ZnIn2S4 can only reach 0.53 mmol g. -1 h -1 Its photocatalytic hydrogen evolution performance is far lower than that of Example 1.

[0050] Comparative Example 2

[0051] This comparative example provides a photocatalyst with a noble metal co-catalyst supported by ultrasound or photodeposition alone. The preparation steps of the photocatalyst with the noble metal co-catalyst supported by ultrasound are as follows:

[0052] (1) ZnIn2S4 / ZnS with spherical nanoflowers were prepared by the same method as in Example 1.

[0053] (2) The difference from Example 1 is that after argon purification, solution B was treated with ultrasound at an intensity of 180 W for 30 minutes, without visible light irradiation. The remaining steps were the same as in Example 1, and the final sample was named ZnIn2S4 / ZnS-U.

[0054] The preparation steps of the photocatalyst with photodeposition supported noble metal co-catalyst are as follows:

[0055] (1) ZnIn2S4 / ZnS with spherical nanoflowers were prepared by the same method as in Example 1.

[0056] (2) The difference from Example 1 is that after argon purification, solution B was irradiated with visible light (λ > 420 nm, xenon lamp light source) for 30 min, without ultrasonic treatment. The remaining steps are the same as in Example 1, and the final sample was named ZnIn2S4 / ZnS-Pt.

[0057] The hydrogen evolution performance test method was the same as in Example 1. The hydrogen evolution performance of ZnIn2S4 / ZnS-U and ZnIn2S4 / ZnS-Pt were 4.28 mmol g. -1 h -1 and 10.88 mmol g -1 h -1 For details, please see Figure 3 .

[0058] Example 2

[0059] This embodiment provides a photocatalyst supported on a noble metal co-catalyst by ultrasound-assisted photodeposition with different volumes of co-catalyst precursors. The preparation steps of the ultrasound-supported noble metal co-catalyst photocatalyst are the same as those in Example 1, except that 0 (i.e., the blank control of Comparative Example 1), 10, 20, 30, 60, 80, 100, 130, and 200 μL of H2PtCl6·6H2O were added at a concentration of 1.5 mg / mL. -1 The corresponding hydrogen evolution performance of ZnIn2S4 / ZnS-UPt at the given concentrations were 8.884, 16.43, 22.43, 18.68, 17.38, 16.62, 15.96, and 11.08 mmol g, respectively. -1 h -1 For details, please see Figure 4Furthermore, ICP tests were performed on photocatalysts with precursor addition volumes of 10, 30, 80, 130, and 200 μL, yielding Pt mass fractions of 0.024%, 0.084%, 0.22%, 0.341%, and 0.545%, respectively. Detailed results are shown in [link to results]. Figure 5 Among them, the ZnIn2S4 / ZnS-UPt sample with a loading of 0.084% exhibited the highest photocatalytic hydrogen production performance.

[0060] Example 3

[0061] This embodiment provides ZnIn2S4 / ZnS-UPt photocatalysts prepared under different ultrasonic treatment conditions. The specific steps are as follows:

[0062] (1) ZnIn2S4 / ZnS with spherical nanoflowers were prepared by the same method as in Example 1.

[0063] (2) 20 mg of ZnIn2S4 / ZnS water splitting photocatalyst powder was added to 5 mL of triethanolamine (TEOA) and 45 mL of deionized water, and the mixture was stirred for 10 min (named Solution A). Then, 30 μL of chloroplatinic acid hydrate solution (H2PtCl6·6H2O) was added dropwise to Solution A using a pipette to obtain Solution B. Solution B was purified by argon gas for 30 min to achieve complete removal of dissolved oxygen and establish anaerobic conditions. Then, synchronous ultrasound and visible light irradiation were applied to promote platinum deposition.

[0064] Repeat the above steps to prepare multiple portions of solution B for later use.

[0065] At room temperature, the ultrasonic probe was positioned 2 cm below the surface of the suspension in each solution B, and the ultrasonic intensities were set to 0 W, 90 W, 180 W, 270 W, and 360 W, respectively. Simultaneous visible light irradiation (λ > 420 nm, xenon lamp source) was applied throughout the ultrasonic treatment. After 30 min of ultrasonic and light treatment, the samples were centrifuged and washed twice with deionized water and ethanol, then freeze-dried. The resulting samples were subjected to hydrogen evolution performance testing, using the same method as in Example 1.

[0066] At room temperature, the ultrasonic probe was positioned 2 cm below the surface of the suspension in each solution B, and the ultrasonic intensity was set to 180 W. Simultaneous visible light irradiation (λ > 420 nm, xenon lamp source) was applied throughout the ultrasonic treatment. After ultrasonic and light treatments for 10 min, 20 min, 30 min, 40 min, and 50 min respectively, the samples were centrifuged and washed twice with deionized water and ethanol, then freeze-dried. The resulting samples were then subjected to hydrogen evolution performance testing, using the same method as in Example 1.

[0067] from Figure 6 It can be seen that the photocatalyst prepared under ultrasonic-assisted light irradiation conditions with an ultrasonic power of 180 W and a duration of 30 min exhibits the best performance.

[0068] Example 4

[0069] This embodiment provides ZnIn2S4 / CdS, ZnIn2S4 / MoS2, and ZnIn2S4 / In2S3 heterojunctions with supported cocatalysts via ultrasound-assisted photodeposition. The specific preparation steps are as follows:

[0070] 20 mg of ZnIn2S4 / CdS, ZnIn2S4 / MoS2, and ZnIn2S4 / In2S3 water splitting photocatalyst powders were added to 5 mL of triethanolamine (TEOA) and 45 mL of deionized water, respectively, and the mixture was stirred for 10 min (designated as solution A). Then, 30 μL of chloroplatinic acid hydrate solution (H2PtCl6·6H2O) was added dropwise to solution A using a pipette to obtain solution B. Solution B was purified by argon gas for 30 min to achieve complete dissolved oxygen removal and establish anaerobic conditions. Synchronous ultrasound and visible light irradiation were then applied to promote platinum deposition. The ultrasound probe was positioned 2 cm below the surface of the suspension, and the ultrasound intensity was 180 W. Synchronous visible light irradiation (λ > 420 nm, xenon lamp source) was applied throughout the ultrasound treatment. After 30 min of ultrasound and light treatment, the sample was centrifuged and washed twice with deionized water and ethanol, and then freeze-dried. The obtained samples were named ZnIn2S4 / CdS-UPt, ZnIn2S4 / MoS2-UPt, and ZnIn2S4 / In2S3-UPt, respectively. The hydrogen evolution performance of these samples was tested using the same methods as in Example 1.

[0071] XRD patterns of ZnIn2S4 / CdS, ZnIn2S4 / MoS2, and ZnIn2S4 / In2S3 water splitting photocatalysts are shown below. Figure 7 As shown, the successful construction of the heterostructure is confirmed.

[0072] The hydrogen evolution performance of ZnIn2S4 / CdS-UPt, ZnIn2S4 / MoS2-UPt, and ZnIn2S4 / In2S3-UPt can reach 5.08, 14.59, and 1.1 mmol g, respectively. -1 h -1 .

[0073] Comparative Example 3

[0074] This comparative example provides a ZnIn2S4 / CdS, ZnIn2S4 / MoS2, and ZnIn2S4 / In2S3 photocatalyst, which are identical to the ZnIn2S4 / CdS, ZnIn2S4 / MoS2, and ZnIn2S4 / In2S3 water splitting photocatalysts in Example 4. The hydrogen evolution performance of these photocatalysts was tested using the same methods as in Example 1.

[0075] The hydrogen evolution performance of the ZnIn2S4 / CdS, ZnIn2S4 / MoS2, and ZnIn2S4 / In2S3 photocatalysts were 0.23, 2.83, and 0.17 mmol g, respectively. -1 h -1 .

[0076] Comparative Example 4

[0077] This comparative example provides a photocatalyst with a noble metal co-catalyst supported only by photodeposition. The difference from Example 4 is that solution B, after argon purification, is only irradiated with visible light for 30 minutes, without ultrasonic treatment. The remaining steps are the same as in Example 4. The final prepared samples are named ZnIn2S4 / CdS-Pt, ZnIn2S4 / MoS2-Pt, and ZnIn2S4 / In2S3-Pt, respectively. The hydrogen evolution performance of these samples was tested using the same methods as in Example 1.

[0078] The hydrogen evolution performance of ZnIn2S4 / CdS-Pt, ZnIn2S4 / MoS2-Pt, and ZnIn2S4 / In2S3-Pt were 2.16, 9.95, and 0.55 mmol g, respectively. -1 h -1 .

[0079] like Figure 8 As shown, the photocatalysts prepared in Example 4 exhibit significantly better performance than those prepared in Comparative Examples 3 and 4. This is because the ultrasonic-assisted and photodeposition loading methods used in Example 3 have a synergistic effect. The photocatalysts formed by the combined treatment of these two methods have strong interfacial Pt-S bonds. The ultrasonic-induced interfacial defects serve as sites for Pt co-catalyst loading, thereby forming a higher quality photocatalyst / co-catalyst interface, reducing interfacial recombination, and thus improving the stability of the co-catalyst during the reaction process. This prevents aggregation and detachment, enabling the catalytic system to maintain high efficiency for a long time.

Claims

1. A method for the preparation of an ultrasonic-assisted photodeposition of a supported heterojunction of a cocatalyst, characterized in that, Includes the following steps: ZnIn2S4 / metal sulfide heterojunction and triethanolamine were added to water and mixed thoroughly to obtain solution A; Platinum source solution is added dropwise to solution A to obtain solution B, thus removing dissolved oxygen from solution B; Solution B was placed in an ultrasonic environment and simultaneously irradiated with visible light. After the reaction was completed, the product was collected, which is the heterojunction of the ultrasonic-assisted photodeposition supported catalyst.

2. The method of claim 1, wherein the method is characterized by: ZnIn2S4 / metal sulfide heterojunctions are selected from: ZnIn2S4 / ZnS, ZnIn2S4 / CdS, ZnIn2S4 / MoS2, and ZnIn2S4 / In2S3.

3. The method of claim 2, wherein the method is characterized by: In the heterojunction with ultrasonic-assisted photodeposition supported catalyst, the loading of platinum accounts for 0.024-0.545% of the total mass of the heterojunction.

4. The method of claim 2, wherein the method is characterized by, The preparation method of ZnIn2S4 / ZnS heterojunction is as follows: Zinc sulfate hydrate and indium trichloride hydrate were dissolved in water and glycerol and stirred to obtain a mixture. Thioacetamide was added to the mixture and stirred to obtain a clear precursor liquid. The clear precursor liquid was subjected to a hydrothermal reaction. After the reaction was completed, the product was collected to obtain the ZnIn2S4 / ZnS heterojunction.

5. The method for preparing a heterojunction of a catalyst supported by ultrasound-assisted photodeposition according to claim 1, characterized in that, The platinum source is selected from: chloroplatinic acid hexahydrate, tetraammineplatinum nitrate, tetraammineplatinum chloride, potassium chloroplatinate, and sodium chloroplatinate.

6. The method for preparing a heterojunction of a catalyst supported by ultrasound-assisted photodeposition according to claim 1, characterized in that, Solution B is purified by argon gas to remove dissolved oxygen from solution B.

7. The method for preparing a heterojunction of a catalyst supported by ultrasound-assisted photodeposition according to claim 1, characterized in that, Solution B was placed in an ultrasonic environment with an ultrasonic intensity of 90-360W and an ultrasonic time of 10-50 min.

8. The method for preparing a heterojunction of a catalyst supported by ultrasound-assisted photodeposition according to claim 1, characterized in that, In visible light irradiation, the wavelength of visible light is greater than 420 nm, and the irradiation time is 20-40 min.

9. A heterojunction of an ultrasonic-assisted photodeposition supported catalyst prepared by the preparation method according to any one of claims 1-8.

10. The use of the heterojunction of claim 9 in the preparation of a photocatalyst for hydrogen production.

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