Preparation method and application of SnIn4S8-coated FeNi2P hollow nanorod composite material

Abstract

The invention provides a SnIn4S8-coated FeNi2P hollow nanorod composite material and a preparation method thereof. The photocatalytic hydrogen production performance and the stability of the SnIn4S8-coated FeNi2P hollow nanorod composite material are researched. The preparation method of the SnIn4S8-coated FeNi2P comprises the following steps: synthesizing a FeNi2-MIL-88 nanorod with a hollow structure by adopting a hydrothermal method, and then obtaining the FeNi2P by adopting a gas phase phosphating method. And finally, coating the surface of the FeNi2P with SnIn4S8 by virtue of an in-situ growth method, so as to obtain the SnIn4S8-coated FeNi2P hollow nanorod composite material. The result shows that the hydrogen production amount of the SnIn4S8-coated FeNi2P within 3 hours reaches 18083.93 [mu] mol / g, and the SnIn4S8-coated FeNi2P has good cycle stability.

Description

Technical Field

[0001] The present invention relates to the field of photocatalysis technology, and in particular to a SnIn 4 S 8 @FeNi 2 Preparation and photocatalytic application of P hollow nanorod composites. Background Art

[0002] The shortage of fossil fuels and environmental pollution have prompted the continuous research and development of new renewable energy sources. Among them, hydrogen energy has attracted much attention due to its advantages such as clean, zero pollution and non-toxicity. Since solar energy resources are abundant and can be obtained locally, the use of solar energy to produce hydrogen has a good prospect. Under light conditions, photocatalysts can use solar energy to split water to produce hydrogen, but in this process there are still problems such as low catalyst light utilization, 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 structured metal organic frameworks (MOFs) are a type of porous material with low density and stable morphology. The hollow structure improves the light-harvesting ability and reduces the migration distance of the carrier. Transition metal phosphides derived from MOFs can retain their hollow porous structure and improve their stability, and have been widely used in the field of photocatalytic hydrogen production. However, transition metal phosphides still have disadvantages such as poor dispersibility and low carrier separation rate. Their catalytic performance can be improved by ion doping, morphology regulation, heterostructure construction, and co-catalyst loading. Among them, constructing a heterostructure is an effective way to improve the efficiency of photogenerated carrier separation.

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

[0005] In order to solve the shortcomings of the prior art, the present invention firstly adopts a hydrothermal method to synthesize a hollow structure FeNi 2 -MIL-88 nanorods, and then FeNi was obtained by vapor phase phosphating 2 P, and secondly, SnIn with high electronegativity and strong light absorption ability 4 S 8 Nanosheets grown in situ on FeNi 2 P surface, forming SnIn 4 S 8 @FeNi 2 P hollow nanorod composites. The constructed heterostructure effectively inhibits the recombination of photogenerated electrons and holes, thereby improving the photocatalytic hydrogen production performance.

[0006] Specifically, the present invention provides a SnIn 4 S8 @FeNi 2 P hollow nanorod composites, first synthesized FeNi 2 -MIL-88 nanorods, which were then phosphated to form FeNi 2 P, finally in FeNi 2 In situ growth of a SnIn layer on the P surface 4 S 8 , get SnIn 4 S 8 @FeNi 2 P hollow nanorod composites.

[0007] Another object of the present invention is to provide a SnIn 4 S 8 @FeNi 2 The preparation method of the P hollow nanorod composite material specifically comprises the following steps:

[0008] (1) 1,4-Benzenedicarboxylic acid, ferric chloride and nickel nitrate hexahydrate are dissolved in dimethylacetamide in sequence and stirred to fully dissolve. The above solution is added into a high pressure reactor and heated at 150° C. for 3 h. The product is centrifuged, washed and dried to obtain FeNi 2 -MIL-88 hollow nanorods;

[0009] (2) FeNi 2 -MIL-88 nanorods and anhydrous sodium hypophosphite were placed in two porcelain boats respectively. The porcelain boat containing anhydrous sodium hypophosphite was placed at the air inlet end of the tube furnace. 2 -MIL-88 porcelain boat is placed at the outlet of the tube furnace. 2 The temperature was raised to 350 °C and maintained for 2 h to obtain FeNi 2 P hollow nanorods;

[0010] (3) FeNi 2 The P hollow nanorods were dissolved in ethanol and ultrasonicated for 10 min. Tin tetrachloride pentahydrate and indium trichloride tetrahydrate were added in sequence and stirred to dissolve. Then, thioacetamide was added. The mixed solution was heated under reflux for 3 h. The product was centrifuged, washed and dried to obtain SnIn 4 S 8 @FeNi 2 P hollow nanorod composites.

[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), FeNi 2The mass ratio of P to anhydrous sodium hypophosphite is 1:(1-3).

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

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

[0015] Preferably, in step (3), FeNi 2 The P content is 2-12 g / L.

[0016] Another object of the present invention is to provide a SnIn 4 S 8 @FeNi 2 Application of P hollow nanorod composites in photocatalytic water splitting to produce hydrogen.

[0017] A 300W full-spectrum Xe lamp was used as the light source to produce hydrogen by photocatalysis at a certain wavelength (≥420nm). 10mg of photocatalyst was added to a glass container containing 90mL of deionized water, 10mL of triethanolamine, and 0.033g of eosin. During the test, the system temperature was maintained at around 6°C. Finally, the data was analyzed using a gas chromatograph (GC-2014).

[0018] Compared with the prior art, the SnIn 4 S 8 @FeNi 2 P hollow nanorod composite material, the preparation time is short and the method is simple, the SnIn prepared by the present invention 4 S 8 @FeNi 2 As a photocatalyst, the P hollow nanorod composite material has significantly improved hydrogen production performance by water splitting and has good cycle stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The FeNi described in Example 1 2 - Transmission electron microscope photo of MIL-88.

[0020] Figure 2 SnIn described in Example 3 4 S 8 @FeNi 2 Scanning electron micrograph of P.

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

[0022] Figure 4 SnIn described in Example 3 4 S 8 @FeNi 2 XRD spectrum of P. DETAILED DESCRIPTION

[0023] The present invention will be further described below in conjunction with specific embodiments:

[0024] Example 1

[0025] This embodiment provides a FeNi 2 -The preparation method of MIL-88 nanorods comprises the following steps:

[0026] 1 mmol of 1,4-benzenedicarboxylic acid, 0.33 mmol of ferric chloride and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide in sequence and stirred to fully dissolve. The above 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 FeNi 2 -MIL-88 hollow nanorods.

[0027] Example 2

[0028] This embodiment provides a FeNi 2 The preparation method of P comprises the following steps:

[0029] 30 mg of FeNi 2 -MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two porcelain boats respectively. The porcelain boat containing anhydrous sodium hypophosphite was placed at the air inlet end of the tube furnace. 2 -MIL-88 porcelain boat is placed at the outlet of the tube furnace. 2 The temperature was raised to 350 °C and maintained for 2 h at a heating rate of 3 °C / min to obtain FeNi 2 P hollow nanorods.

[0030] Example 3

[0031] This embodiment provides a SnIn 4 S 8 @FeNi 2 The preparation method of the P hollow nanorod composite material comprises the following steps:

[0032] (1) 1 mmol of 1,4-benzenedicarboxylic acid, 0.33 mmol of ferric chloride, and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide in sequence, stirred to fully dissolve, and the above solution was added to a high-pressure reactor, heated at 150° C. for 3 h, and the product was centrifuged, washed, and dried to obtain FeNi 2 -MIL-88 hollow nanorods.

[0033] (2) 30 mg of FeNi 2 -MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two porcelain boats respectively. The porcelain boat containing anhydrous sodium hypophosphite was placed at the air inlet end of the tube furnace. 2 -MIL-88 porcelain boat is placed at the outlet of the tube furnace. 2 The temperature was raised to 350 °C and maintained for 2 h at a heating rate of 3 °C / min to obtain FeNi 2 P hollow nanorods.

[0034] (3) 100 mg of FeNi 2 The P hollow nanorods were dissolved in 12.5 mL of ethanol and ultrasonicated for 10 min. 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate were added in sequence and stirred to dissolve. Then 1.5 mmol of thioacetamide was added. The mixed solution was heated under reflux for 3 h. The product was centrifuged, washed and dried to obtain SnIn 4 S 8 @FeNi 2 P hollow nanorod composites.

[0035] The FeNi prepared in Example 1 2 -MIL-88 nanorods were tested by transmission electron microscopy. The test results are shown in Figure 1 As shown in the figure, FeNi 2 -MIL-88 exhibits a hollow nanorod structure.

[0036] The SnIn prepared in Example 3 4 S 8 @FeNi 2 P was tested by scanning electron microscope, and the test results are shown in Figure 2 , as shown in the figure, SnIn 4 S 8 Successfully coated on FeNi 2 P surface and SnIn 4 S 8 @FeNi 2 P still maintains the hollow nanorod structure.

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

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

[0039] 2. When the SnIn prepared in Example 3 is used 4 S 8 @FeNi 2 When P was used as the photocatalyst, the photocatalytic hydrogen production was 18083.93 μmol / g within 3 hours.

[0040] The SnIn prepared in Example 3 4 S 8 @FeNi 2 P composite material was subjected to XRD test, and the test results are shown in Figure 4 , as shown in the figure, in SnIn 4 S 8 @FeNi 2 In the XRD pattern of P, it is observed that 4 S 8 and FeNi 2 The diffraction peaks corresponding to P and no other impurity peaks further confirm that SnIn 4 S 8 @FeNi 2 P composite material was successfully prepared.

[0041] The above experimental results show that FeNi 2 P surface modified SnIn 4 S 8 After that, the photocatalytic hydrogen production performance was significantly improved, proving that FeNi 2 P and SnIn 4 S 8 The composite can effectively enhance the photocatalytic hydrogen production performance.

[0042] Example 4

[0043] This embodiment provides a SnIn 4 S 8 @FeNi 2The preparation method of the P hollow nanorod composite material comprises the following steps:

[0044] (1) 1 mmol of 1,4-benzenedicarboxylic acid, 0.33 mmol of ferric chloride, and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide in sequence, stirred to fully dissolve, and the above solution was added to a high-pressure reactor, heated at 150° C. for 3 h, and the product was centrifuged, washed, and dried to obtain FeNi 2 -MIL-88 hollow nanorods.

[0045] (2) 30 mg of FeNi 2 -MIL-88 nanorods and 60 mg of anhydrous sodium hypophosphite were placed in two porcelain boats respectively. The porcelain boat containing anhydrous sodium hypophosphite was placed at the air inlet end of the tube furnace. 2 -MIL-88 porcelain boat is placed at the outlet of the tube furnace. 2 The temperature was raised to 350 °C and maintained for 2 h at a heating rate of 3 °C / min to obtain FeNi 2 P hollow nanorods.

[0046] (3) 100 mg of FeNi 2 The P hollow nanorods were dissolved in 12.5 mL of ethanol and ultrasonicated for 10 min. 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate were added in sequence and stirred to dissolve. Then 1.5 mmol of thioacetamide was added. The mixed solution was heated under reflux for 3 h. The product was centrifuged, washed and dried to obtain SnIn 4 S 8 @FeNi 2 P hollow nanorod composites.

[0047] Example 5

[0048] This embodiment provides a SnIn 4 S 8 @FeNi 2 The preparation method of the P hollow nanorod composite material comprises the following steps:

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

[0050] (2) 30 mg of FeNi 2-MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two porcelain boats respectively. The porcelain boat containing anhydrous sodium hypophosphite was placed at the air inlet end of the tube furnace. 2 -MIL-88 porcelain boat is placed at the outlet of the tube furnace. 2 The temperature was raised to 350 °C and maintained for 2 h at a heating rate of 1 °C / min to obtain FeNi 2 P hollow nanorods.

[0051] (3) 100 mg of FeNi 2 The P hollow nanorods were dissolved in 12.5 mL of ethanol and ultrasonicated for 10 min. 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate were added in sequence and stirred to dissolve. Then 1.5 mmol of thioacetamide was added. The mixed solution was heated under reflux for 3 h. The product was centrifuged, washed and dried to obtain SnIn 4 S 8 @FeNi 2 P hollow nanorod composites.

[0052] Example 6

[0053] This embodiment provides a SnIn 4 S 8 @FeNi 2 The preparation method of the P hollow nanorod composite material comprises the following steps:

[0054] (1) 1 mmol of 1,4-benzenedicarboxylic acid, 0.33 mmol of ferric chloride, and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide in sequence, stirred to fully dissolve, and the above solution was added to a high-pressure reactor, heated at 150° C. for 3 h, and the product was centrifuged, washed, and dried to obtain FeNi 2 -MIL-88 hollow nanorods.

[0055] (2) 30 mg of FeNi 2 -MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two porcelain boats respectively. The porcelain boat containing anhydrous sodium hypophosphite was placed at the air inlet end of the tube furnace. 2 -MIL-88 porcelain boat is placed at the outlet of the tube furnace. 2 The temperature was raised to 350 °C and maintained for 2 h at a heating rate of 3 °C / min to obtain FeNi 2 P hollow nanorods.

[0056] (3) 100 mg of FeNi 2The P hollow nanorods were dissolved in 12.5 mL of ethanol and ultrasonicated for 10 min. 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate were added in sequence and stirred to dissolve. Then 1.0 mmol of thioacetamide was added. The mixed solution was heated under reflux for 3 h. The product was centrifuged, washed and dried to obtain SnIn 4 S 8 @FeNi 2 P hollow nanorod composites.

[0057] Example 7

[0058] This embodiment provides a SnIn 4 S 8 @FeNi 2 The preparation method of the P hollow nanorod composite material comprises the following steps:

[0059] (1) 1 mmol of 1,4-benzenedicarboxylic acid, 0.33 mmol of ferric chloride, and 0.66 mmol of nickel nitrate hexahydrate were dissolved in 30 mL of dimethylacetamide in sequence, stirred to fully dissolve, and the above solution was added to a high-pressure reactor, heated at 150° C. for 3 h, and the product was centrifuged, washed, and dried to obtain FeNi 2 -MIL-88 hollow nanorods.

[0060] (2) 30 mg of FeNi 2 -MIL-88 nanorods and 90 mg of anhydrous sodium hypophosphite were placed in two porcelain boats respectively. The porcelain boat containing anhydrous sodium hypophosphite was placed at the air inlet end of the tube furnace. 2 -MIL-88 porcelain boat is placed at the outlet of the tube furnace. 2 The temperature was raised to 350 °C and maintained for 2 h at a heating rate of 3 °C / min to obtain FeNi 2 P hollow nanorods.

[0061] (3) 150 mg of FeNi 2 The P hollow nanorods were dissolved in 12.5 mL of ethanol and ultrasonicated for 10 min. 0.125 mmol of tin tetrachloride pentahydrate and 0.5 mmol of indium trichloride tetrahydrate were added in sequence and stirred to dissolve. Then 1.5 mmol of thioacetamide was added. The mixed solution was heated under reflux for 3 h. The product was centrifuged, washed and dried to obtain SnIn 4 S 8 @FeNi 2 P hollow nanorod composites.

[0062] The above is only a preferred embodiment of the present invention, and does not limit the present invention in other forms. Any technician familiar with the profession may use the above disclosed technical content to change or modify it into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the technical solution of the present invention still belongs to the protection scope of the technical solution of the present invention.

Claims

1. A SnIn 4 S 8 @FeNi 2 Preparation method of P hollow nanorod composite material, It is characterized in that The following steps are involved: (1) 1,4-Benzenedicarboxylic acid, ferric chloride and nickel nitrate hexahydrate are dissolved in dimethylacetamide in sequence and stirred to fully dissolve. The above solution is added into a high pressure reactor and heated at 150° C. for 3 h. The product is centrifuged, washed and dried to obtain FeNi 2 -MIL-88 hollow nanorods; (2) FeNi 2 -MIL-88 nanorods and anhydrous sodium hypophosphite were placed in two porcelain boats respectively. The porcelain boat containing anhydrous sodium hypophosphite was placed at the air inlet end of the tube furnace. 2 -MIL-88 porcelain boat is placed at the outlet of the tube furnace. 2 The temperature was raised to 350 °C and maintained for 2 h to obtain FeNi 2 P hollow nanorods; (3) FeNi 2 The P hollow nanorods were dissolved in ethanol and ultrasonicated for 10 min. Tin tetrachloride pentahydrate and indium trichloride tetrahydrate were added in sequence and stirred to dissolve. Then, thioacetamide was added. The mixed solution was heated under reflux for 3 h. The product was centrifuged, washed and dried to obtain SnIn 4 S 8 @FeNi 2 P hollow nanorod composites.

2. SnIn as claimed in claim 1 4 S 8 @FeNi 2 Preparation method of P, It is characterized in that In the step (1), the molar ratio of 1,4-phthalic acid, ferric chloride and nickel nitrate hexahydrate is (2-8):1:(1-2).

3. SnIn as claimed in claim 1 4 S 8 @FeNi 2 Preparation method of P, It is characterized in that In the step (2), FeNi 2 -The mass ratio of MIL-88 to anhydrous sodium hypophosphite is 1:(1-3).

4. SnIn as claimed in claim 1 4 S 8 @FeNi 2 Preparation method of P, It is characterized in that The heating rate of high temperature calcination in step (2) is 1 to 5°C / min.

5. SnIn as claimed in claim 1 4 S 8 @FeNi 2 Preparation method of P, It is characterized in that In the step (3), the molar ratio of tin tetrachloride pentahydrate, indium trichloride tetrahydrate and thioacetamide is 0.25:1:(2-5).

6. SnIn as claimed in claim 1 4 S 8 @FeNi 2 Preparation method of P, It is characterized in that In the step (3), FeNi 2 The P content is 2-12 g / L.

7. SnIn as claimed in claim 1 4 S 8 @FeNi 2 Application of P hollow nanorod composites in photocatalytic hydrogen production.

Images