A method for preparing SnIn4S8@FeNi2P hollow nanorod composite materials and its application

Abstract

This invention provides a SnIn4S8@FeNi2P hollow nanorod composite material and its preparation method, and investigates its photocatalytic hydrogen production performance and stability. The preparation method of SnIn4S8@FeNi2P is as follows: hollow FeNi2-MIL-88 nanorods were synthesized by a hydrothermal method, and then FeNi2P was obtained by a gas-phase phosphating method. Finally, SnIn4S8 was coated onto the surface of FeNi2P by in-situ growth to obtain the SnIn4S8@FeNi2P hollow nanorod composite material. The results show that SnIn4S8@FeNi2P achieves a hydrogen production of 18083.93 μmol / g within 3 hours and exhibits good cycling stability.

Description

Technical Field

[0001] This invention relates to the field of photocatalysis technology, and in particular to the preparation of a SnIn4S8@FeNi2P hollow nanorod composite material and its photocatalytic application. Background Technology

[0002] The shortage of fossil fuels and environmental pollution have spurred continuous research and development of new renewable energy sources. Among these, hydrogen energy has attracted significant attention due to its clean, zero-pollution, and non-toxic properties. Given the abundance and local availability of solar energy resources, using solar energy to produce hydrogen shows great promise. Under sunlight, photocatalysts can utilize solar energy to split water and produce hydrogen; however, this process still faces challenges such as low light utilization rate of the catalyst, poor structural stability, and low carrier separation efficiency. Therefore, exploring photocatalysts with high activity and high stability has become a research hotspot in this field.

[0003] Hollow metal-organic frameworks (MOFs) are low-density, morphology-stable porous materials. Their hollow structure enhances light-harvesting ability and reduces the migration distance of the support. Derivatizing transition metal phosphides from MOFs retains their hollow porous structure while improving their stability, leading to their widespread application in photocatalytic hydrogen production. However, transition metal phosphides still suffer from poor dispersibility and low carrier separation efficiency. Their catalytic performance can be improved through ion doping, morphology manipulation, heterostructure construction, and co-catalyst loading. Among these methods, constructing heterostructures is an effective way to improve the separation efficiency of photogenerated carriers.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention first synthesizes hollow FeNi2-MIL-88 nanorods using a hydrothermal method, then obtains FeNi2P via a gas-phase phosphating method. Next, SnIn4S8 nanosheets with high electronegativity and strong light absorption are grown in situ on the FeNi2P surface to form a SnIn4S8@FeNi2P hollow nanorod composite material. The constructed heterostructure effectively suppresses the recombination of photogenerated electrons and holes, thereby improving the photocatalytic hydrogen production performance.

[0006] Specifically, the present invention provides a SnIn4S8@FeNi2P hollow nanorod composite material. First, FeNi2-MIL-88 nanorods are synthesized, then they are phosphated to form FeNi2P, and finally a layer of SnIn4S8 is grown in situ on the surface of FeNi2P to obtain the SnIn4S8@FeNi2P hollow nanorod composite material.

[0007] Another objective of this invention is to provide a method for preparing the above-mentioned SnIn4S8@FeNi2P hollow nanorod composite material, specifically including the following steps:

[0008] (1) 1,4-phenylenediamine, ferric chloride and nickel nitrate hexahydrate were dissolved in dimethylacetamide in sequence and stirred until fully dissolved. The solution was added to a high-pressure reactor and heated at 150°C for 3 hours. The product was centrifuged, washed and dried to obtain FeNi2-MIL-88 hollow nanorods.

[0009] (2) FeNi2-MIL-88 nanorods and anhydrous sodium hypophosphite were placed in two separate ceramic boats. The ceramic boat containing anhydrous sodium hypophosphite was placed at the inlet of a tube furnace, and the ceramic boat containing FeNi2-MIL-88 was placed at the outlet of the tube furnace. The temperature was raised to 350℃ under N2 atmosphere and held for 2 hours to obtain FeNi2P hollow nanorods.

[0010] (3) Dissolve FeNi2P hollow nanorods in ethanol, sonicate for 10 min, add tin tetrachloride pentahydrate and indium trichloride tetrahydrate in sequence, stir to dissolve, then add thioacetamide, heat the mixed solution under reflux for 3 h, centrifuge, wash and dry the product to obtain SnIn4S8@FeNi2P hollow nanorod composite material.

[0011] Preferably, in step (1), the molar ratio of 1,4-phthalic acid, ferric chloride and nickel nitrate hexahydrate is (2-8):1:(1-2).

[0012] Preferably, in step (2), the mass ratio of FeNi2P to anhydrous sodium hypophosphite is 1:(1-3).

[0013] Preferably, the heating rate of the high-temperature calcination in step (2) is 1 to 5 °C / min.

[0014] Preferably, the molar ratio of tin tetrachloride pentahydrate, indium trichloride tetrahydrate, and thioacetamide in step (3) is 0.25:1:(2-5).

[0015] Preferably, the FeNi2P content in step (3) is 2-12 g / L.

[0016] Another objective of this invention is to provide an application of the above-mentioned SnIn4S8@FeNi2P hollow nanorod composite material in photocatalytic water splitting for hydrogen production.

[0017] Photocatalytic hydrogen production was performed using a 300W full-spectrum Xe lamp as the light source at a specific wavelength (≥420nm). 10mg of photocatalyst was added to a glass container containing 90mL of deionized water, 10mL of triethanolamine, and 0.033g of eosin. The system temperature was maintained at approximately 6℃ during the test. Finally, the data were analyzed using a gas chromatograph (GC-2014).

[0018] Compared with existing technologies, the SnIn4S8@FeNi2P hollow nanorod composite material provided by this invention has a short preparation time and a simple method. When the SnIn4S8@FeNi2P hollow nanorod composite material prepared by this invention is used as a photocatalyst, its hydrogen production performance through water splitting is significantly improved, and it also has good cycle stability. Attached Figure Description

[0019] Figure 1 The image is a transmission electron microscope (TEM) image of FeNi2-MIL-88 as described in Example 1.

[0020] Figure 2 This is a scanning electron microscope image of SnIn4S8@FeNi2P as described in Example 3.

[0021] Figure 3 The diagram shows the photocatalytic hydrogen production of the catalyst materials prepared in Examples 2 and 3.

[0022] Figure 4 The image shows the XRD pattern of SnIn4S8@FeNi2P as described in Example 3. Detailed Implementation

[0023] The present invention will be further described below with reference to specific embodiments:

[0024] Example 1

[0025] This embodiment provides a method for preparing FeNi2-MIL-88 nanorods, including the following steps:

[0026] 1 mmol of 1,4-phthalic acid, 0.33 mmol of ferric chloride, and 0.66 mmol of nickel nitrate hexahydrate were dissolved sequentially in 30 mL of dimethylacetamide and stirred until fully dissolved. The solution was then added to a high-pressure reactor and heated at 150 °C for 3 h. The product was centrifuged, washed, and dried to obtain FeNi2-MIL-88 hollow nanorods.

[0027] Example 2

[0028] This embodiment provides a method for preparing FeNi2P, including the following steps:

[0029] 30 mg of FeNi2-MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two separate ceramic boats. The boat containing anhydrous sodium hypophosphite was placed at the inlet of a tube furnace, and the boat containing FeNi2-MIL-88 was placed at the outlet. The furnace was heated to 350 °C under a N2 atmosphere and held for 2 h at a heating rate of 3 °C / min to obtain FeNi2P hollow nanorods.

[0030] Example 3

[0031] This embodiment provides a method for preparing SnIn4S8@FeNi2P hollow nanorod composite material, including the following steps:

[0032] (1) 1 mmol of 1,4-phenylenediamine, 0.33 mmol of ferric chloride and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide and stirred until fully dissolved. The solution was added to a high-pressure reactor and heated at 150 °C for 3 h. The product was centrifuged, washed and dried to obtain FeNi2-MIL-88 hollow nanorods.

[0033] (2) 30 mg of FeNi2-MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two separate ceramic boats. The ceramic boat containing anhydrous sodium hypophosphite was placed at the inlet of a tube furnace, and the ceramic boat containing FeNi2-MIL-88 was placed at the outlet of the tube furnace. The temperature was raised to 350 °C under N2 atmosphere and held for 2 h at a heating rate of 3 °C / min to obtain FeNi2P hollow nanorods.

[0034] (3) Dissolve 100 mg of FeNi2P hollow nanorods in 12.5 mL of ethanol, sonicate for 10 min, add 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate in sequence, stir to dissolve, then add 1.5 mmol of thioacetamide, heat the mixed solution under reflux for 3 h, centrifuge, wash and dry the product to obtain SnIn4S8@FeNi2P hollow nanorod composite material.

[0035] Transmission electron microscopy (TEM) was performed on the FeNi2-MIL-88 nanorods prepared in Example 1. The results are shown in the figure. Figure 1 As shown in the figure, FeNi2-MIL-88 exhibits a hollow nanorod structure.

[0036] Scanning electron microscopy (SEM) was performed on the SnIn4S8@FeNi2P prepared in Example 3. The results are shown in [Figure number missing]. Figure 2 As shown in the figure, SnIn4S8 was successfully coated on the FeNi2P surface and SnIn4S8@FeNi2P still maintains the hollow nanorod structure.

[0037] The photocatalytic hydrogen production performance of the products obtained in Examples 2 and 3 was tested. Specifically, a 300W full-spectrum Xe lamp was used as the light source, and photocatalytic hydrogen production was performed at a specific wavelength (≥420nm). 10 mg of photocatalyst was added to a glass container containing 90 mL of deionized water, 10 mL of triethanolamine, and 0.033 g of eosin. During the test, the system temperature was maintained at approximately 6°C. Finally, the data were analyzed using a gas chromatograph (GC-2014), and the results are shown below. Figure 3 As shown in the figure:

[0038] 1. When FeNi2P prepared in Example 2 was used as a photocatalyst, the photocatalytic hydrogen production was 6964.99 μmol / g within 3 hours;

[0039] 2. When SnIn4S8@FeNi2P prepared in Example 3 is used as a photocatalyst, the photocatalytic hydrogen production is 18083.93 μmol / g within 3 hours.

[0040] XRD tests were performed on the SnIn4S8@FeNi2P composite material prepared in Example 3. The test results are shown in [Figure 1]. Figure 4 As shown in the figure, in the XRD pattern of SnIn4S8@FeNi2P, diffraction peaks corresponding to SnIn4S8 and FeNi2P were observed without other impurity peaks, further confirming the successful preparation of the SnIn4S8@FeNi2P composite material.

[0041] The above experimental results show that the photocatalytic hydrogen production performance is significantly improved after FeNi2P is modified with SnIn4S8, proving that the composite of FeNi2P and SnIn4S8 can effectively enhance the photocatalytic hydrogen production performance.

[0042] Example 4

[0043] This embodiment provides a method for preparing SnIn4S8@FeNi2P hollow nanorod composite material, including the following steps:

[0044] (1) 1 mmol of 1,4-phenylenediamine, 0.33 mmol of ferric chloride and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide and stirred until fully dissolved. The solution was added to a high-pressure reactor and heated at 150 °C for 3 h. The product was centrifuged, washed and dried to obtain FeNi2-MIL-88 hollow nanorods.

[0045] (2) 30 mg of FeNi2-MIL-88 nanorods and 60 mg of anhydrous sodium hypophosphite were placed in two separate ceramic boats. The ceramic boat containing anhydrous sodium hypophosphite was placed at the inlet of a tube furnace, and the ceramic boat containing FeNi2-MIL-88 was placed at the outlet of the tube furnace. The temperature was raised to 350 °C under N2 atmosphere and held for 2 h at a heating rate of 3 °C / min to obtain FeNi2P hollow nanorods.

[0046] (3) Dissolve 100 mg of FeNi2P hollow nanorods in 12.5 mL of ethanol, sonicate for 10 min, add 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate in sequence, stir to dissolve, then add 1.5 mmol of thioacetamide, heat the mixed solution under reflux for 3 h, centrifuge, wash and dry the product to obtain SnIn4S8@FeNi2P hollow nanorod composite material.

[0047] Example 5

[0048] This embodiment provides a method for preparing SnIn4S8@FeNi2P hollow nanorod composite material, including the following steps:

[0049] (1) 2 mmol of 1,4-phenylenediamine, 0.33 mmol of ferric chloride and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide and stirred until fully dissolved. The solution was added to a high-pressure reactor and heated at 150 °C for 3 h. The product was centrifuged, washed and dried to obtain FeNi2-MIL-88 hollow nanorods.

[0050] (2) 30 mg of FeNi2-MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two separate ceramic boats. The ceramic boat containing anhydrous sodium hypophosphite was placed at the inlet of a tube furnace, and the ceramic boat containing FeNi2-MIL-88 was placed at the outlet of the tube furnace. The temperature was raised to 350 °C under N2 atmosphere and held for 2 h at a heating rate of 1 °C / min to obtain FeNi2P hollow nanorods.

[0051] (3) Dissolve 100 mg of FeNi2P hollow nanorods in 12.5 mL of ethanol, sonicate for 10 min, add 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate in sequence, stir to dissolve, then add 1.5 mmol of thioacetamide, heat the mixed solution under reflux for 3 h, centrifuge, wash and dry the product to obtain SnIn4S8@FeNi2P hollow nanorod composite material.

[0052] Example 6

[0053] This embodiment provides a method for preparing SnIn4S8@FeNi2P hollow nanorod composite material, including the following steps:

[0054] (1) 1 mmol of 1,4-phenylenediamine, 0.33 mmol of ferric chloride and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide and stirred until fully dissolved. The solution was added to a high-pressure reactor and heated at 150 °C for 3 h. The product was centrifuged, washed and dried to obtain FeNi2-MIL-88 hollow nanorods.

[0055] (2) 30 mg of FeNi2-MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two separate ceramic boats. The ceramic boat containing anhydrous sodium hypophosphite was placed at the inlet of a tube furnace, and the ceramic boat containing FeNi2-MIL-88 was placed at the outlet of the tube furnace. The temperature was raised to 350 °C under N2 atmosphere and held for 2 h at a heating rate of 3 °C / min to obtain FeNi2P hollow nanorods.

[0056] (3) Dissolve 100 mg of FeNi2P hollow nanorods in 12.5 mL of ethanol, sonicate for 10 min, add 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate in sequence, stir to dissolve, then add 1.0 mmol of thioacetamide, heat the mixed solution under reflux for 3 h, centrifuge, wash and dry the product to obtain SnIn4S8@FeNi2P hollow nanorod composite material.

[0057] Example 7

[0058] This embodiment provides a method for preparing SnIn4S8@FeNi2P hollow nanorod composite material, including the following steps:

[0059] (1) 1 mmol of 1,4-phenylenediamine, 0.33 mmol of ferric chloride and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide and stirred until fully dissolved. The solution was added to a high-pressure reactor and heated at 150 °C for 3 h. The product was centrifuged, washed and dried to obtain FeNi2-MIL-88 hollow nanorods.

[0060] (2) 30 mg of FeNi2-MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two separate ceramic boats. The ceramic boat containing anhydrous sodium hypophosphite was placed at the inlet of a tube furnace, and the ceramic boat containing FeNi2-MIL-88 was placed at the outlet of the tube furnace. The temperature was raised to 350 °C under N2 atmosphere and held for 2 h at a heating rate of 3 °C / min to obtain FeNi2P hollow nanorods.

[0061] (3) Dissolve 150 mg of FeNi2P hollow nanorods in 12.5 mL of ethanol, sonicate for 10 min, add 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate in sequence, stir to dissolve, then add 1.5 mmol of thioacetamide, heat the mixed solution under reflux for 3 h, centrifuge, wash and dry the product to obtain SnIn4S8@FeNi2P hollow nanorod composite material.

[0062] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing SnIn4S8@FeNi2P hollow nanorod composite material, characterized in that, Includes the following steps: (1) 1,4-phenylenediamine, ferric chloride and nickel nitrate hexahydrate were dissolved in dimethylacetamide in sequence and stirred until fully dissolved. The solution was added to a high-pressure reactor and heated at 150 °C for 3 h. The product was centrifuged, washed and dried to obtain FeNi2-MIL-88 hollow nanorods. (2) FeNi2-MIL-88 nanorods and anhydrous sodium hypophosphite were placed in two ceramic boats respectively. The ceramic boat containing anhydrous sodium hypophosphite was placed at the gas inlet end of the tube furnace, and the ceramic boat containing FeNi2-MIL-88 was placed at the gas outlet end of the tube furnace. The temperature was raised to 350 °C under N2 atmosphere and held for 2 h to obtain FeNi2P hollow nanorods. (3) Dissolve FeNi2P hollow nanorods in ethanol, sonicate for 10 min, add tin tetrachloride pentahydrate and indium trichloride tetrahydrate in sequence, stir to dissolve, then add thioacetamide, heat the mixed solution under reflux for 3 h, centrifuge, wash and dry the product to obtain SnIn4S8@FeNi2P hollow nanorod composite material.

2. The preparation method of the SnIn4S8@FeNi2P hollow nanorod composite material as described in claim 1, characterized in that, In step (1), the molar ratio of 1,4-phthalic acid, ferric chloride and nickel nitrate hexahydrate is (2~8):1:(1~2).

3. The preparation method of the SnIn4S8@FeNi2P hollow nanorod composite material as described in claim 1, characterized in that, In step (2), the mass ratio of FeNi2-MIL-88 to anhydrous sodium hypophosphite is 1:(1~3).

4. The preparation method of the SnIn4S8@FeNi2P hollow nanorod composite material as described in claim 1, characterized in that, The heating rate in step (2) is 1~5 ℃ / min.

5. The preparation method of the SnIn4S8@FeNi2P hollow nanorod composite material as described in claim 1, characterized in that, In step (3), the molar ratio of tin tetrachloride pentahydrate, indium trichloride tetrahydrate, and thioacetamide is 0.25:1:(2~5).

6. The preparation method of the SnIn4S8@FeNi2P hollow nanorod composite material as described in claim 1, characterized in that, The FeNi2P content in step (3) is 2~12 g / L.

7. The application of a SnIn4S8@FeNi2P hollow nanorod composite material in photocatalytic hydrogen production, characterized in that, The SnIn4S8@FeNi2P hollow nanorod composite material is prepared by the preparation method described in claim 1.

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