A two-component multi-shell sulfide hollow nanomaterial, its preparation method and application

Abstract

This invention discloses a two-component multi-shell hollow sulfide nanomaterial, its preparation method, and its applications. The method includes: performing a sulfidation reaction between a cobalt-based binary transition metal glycerate complex and a sulfur source in an organic solvent to prepare the two-component multi-shell hollow sulfide nanomaterial. The preparation method of the two-component multi-shell hollow sulfide nanomaterial provided by this invention is simple, easy to implement, and low in cost; moreover, the prepared two-component multi-shell hollow sulfide nanomaterial exhibits excellent photocatalytic water splitting and hydrogen production activity, with a maximum H2 yield of up to 16.94 mmol·g. ‑1 ·h ‑1 .

Description

Technical Field

[0001] This invention belongs to the field of functional materials technology, and relates to a two-component multi-shell sulfide hollow nanomaterial, its preparation method and application. Background Technology

[0002] Hollow sulfide functional nanomaterials have attracted considerable interest from scientists in many fields, including electronic devices, energy storage, and catalysis, due to their unique physicochemical properties. Over the past decade, researchers have prepared various hollow nanostructures, such as hollow spheres, hollow cubes, and nanotubes, using different methods. However, most common hollow materials are relatively simple, and their composition and cavity structure often lack fine-tuning, thus limiting their performance optimization and application in specific fields. Studies have shown that two-component or multi-component composite materials exhibit significantly better performance than their corresponding single-component materials due to the synergistic effect between the components. Furthermore, compared to single-shell nanomaterials, multi-shell nanomaterials have a larger specific surface area and enhanced light scattering and reflection capabilities, and have become one of the research hotspots in energy conversion and storage. Soft template and hard template methods have been widely used in the synthesis of sulfide hollow materials; however, the preparation of two-component or multi-component multi-shell hollow materials often requires the assistance of etching agents and multi-step reaction processes. Therefore, finding a simple method to synthesize hollow multi-shell materials with two or more components remains a significant challenge.

[0003] In recent years, the rapid depletion of fossil fuels has led to severe energy shortages and environmental pollution. Semiconductor photocatalysis, capable of utilizing renewable solar energy to split water and produce clean hydrogen fuel, is considered one of the most promising approaches to addressing these problems. Based on the synergistic effect of multi-component materials, and the large specific surface area and enhanced light scattering and reflection capabilities of multi-shell nanomaterials, they have shown broad application prospects in photocatalytic reactions. Nevertheless, developing novel two-component multi-shell hollow materials to achieve efficient photocatalytic water splitting for hydrogen production remains a pressing technical challenge. Summary of the Invention

[0004] Studies have found that among visible-light-responsive semiconductor materials, transition metal sulfides, especially cadmium sulfide, are widely used in photocatalytic water splitting for hydrogen production due to their strong visible light absorption and suitable conduction band energy level positions. However, the high photogenerated charge recombination rate and photocorrosion problems of single-component cadmium sulfide significantly reduce photocatalytic activity. Research shows that compared to single-component semiconductor materials, the built-in electric field in semiconductor composite materials can significantly promote charge carrier separation, and the photocorrosion phenomenon of semiconductors can also be well suppressed. Furthermore, in photocatalytic water splitting for hydrogen production, cobalt sulfide, as a co-catalyst, can effectively improve the reaction efficiency. Therefore, designing and synthesizing bicomponent multi-shell hollow sulfide nanomaterials can significantly enhance the performance of photocatalytic water splitting for hydrogen production.

[0005] Based on this, the present invention provides a two-component multi-shell hollow sulfide nanomaterial, its preparation method and application, wherein the two-component multi-shell hollow sulfide nanomaterial has excellent photocatalytic performance, and the preparation method is simple to operate.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows:

[0007] A method for preparing a two-component multi-shell sulfide hollow nanomaterial, the method comprising:

[0008] The bicomponent multi-shell sulfide hollow nanomaterial was prepared by sulfidation reaction of cobalt-based binary transition metal glycerate complex and sulfur source in an organic solvent.

[0009] In this invention, the cobalt-based binary transition metal glycerate complex is prepared using conventional methods in the art. Exemplarily, the cobalt-based binary transition metal glycerate complex is prepared by a solvothermal reaction of a mixture comprising isopropanol, glycerol, and a transition metal salt. Preferably, the preparation method of the cobalt-based binary transition metal glycerate complex is as follows: isopropanol, glycerol, and a transition metal salt are mixed and added to a reaction vessel for a solvothermal reaction; after cooling, the mixture is centrifuged, washed, and dried, and the product is collected to obtain the cobalt-based binary transition metal glycerate complex.

[0010] For example, the transition metal salt is at least one of a transition metal nitrate, chloride, or sulfate. For instance, the transition metal salt is selected from cobalt nitrate, and also from cadmium nitrate, lead nitrate, and copper nitrate.

[0011] According to the present invention, the transition metal in the cobalt-based binary transition metal glycerate complex includes Co, and further includes one of Cd, Pb, and Cu; the transition metal ion includes Co. 2+ It also includes Cd 2+ Pb 2+ Cu 2+One of them, for example, the transition metal ion includes Co. 2+ and Cd 2+ , or Co 2+ and Pb 2+ , or Co 2+ and Cu 2+ .

[0012] According to the present invention, the sulfur source is selected from at least one of thioacetamide, thiourea, and L-cysteine.

[0013] According to the present invention, the mass ratio of the cobalt-based binary transition metal glycerate complex to the sulfur source is 1:0.5-8, preferably 1:1-4.

[0014] According to the present invention, the organic solvent is selected from at least one of methanol, ethanol, and isopropanol.

[0015] According to the present invention, the concentration of the cobalt-based binary transition metal glycerate complex in an organic solvent is 0.001-0.01 g / mL, exemplarily 0.001 g / mL, 0.002 g / mL, 0.003 g / mL, 0.004 g / mL, 0.005 g / mL, 0.006 g / mL, 0.007 g / mL, 0.008 g / mL, 0.009 g / mL or 0.01 g / mL.

[0016] According to the present invention, the sulfidation reaction time is 10 min to 20 h, such as 10 min, 30 min, 3 h, 6 h, 12 h, 15 h, or 20 h, but is not limited to the listed values; other unlisted values ​​within this range are also applicable. Different sulfidation reaction times result in different gap sizes between the shells and different photocatalytic hydrogen production activities.

[0017] According to the present invention, the temperature of the vulcanization reaction is 120-200°C, exemplarily 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C.

[0018] The present invention also provides a two-component multi-shell sulfide hollow nanomaterial prepared by the above method.

[0019] The present invention also provides the application of the above-mentioned two-component multi-shell sulfide hollow nanomaterials in photocatalysts for hydrogen production through water splitting.

[0020] The beneficial effects of this invention are:

[0021] (1) The preparation method of the two-component multi-shell sulfide hollow nanomaterials provided by the present invention is simple, easy to implement and low in cost;

[0022] (2) The bicomponent multi-shell sulfide hollow nanomaterials provided by this invention have excellent photocatalytic water splitting hydrogen production activity, with a maximum H2 yield of 16.94 mmol·g. -1 ·h -1 . Attached Figure Description

[0023] Figure 1 These are transmission electron microscope images of the two-component multi-shell sulfide hollow nanomaterials prepared in Examples 1-3 of this invention;

[0024] Figure 2 These are transmission electron microscope images of the two-component multi-shell sulfide hollow nanomaterials prepared in Examples 1, 4, and 5 of this invention;

[0025] Figure 3 This is a comparison diagram of the hydrogen production activity of the photocatalysts prepared in Examples 1, 4, and 5 of this invention. Detailed Implementation

[0026] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0027] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0028] Example 1

[0029] A method for preparing a two-component multi-shell sulfide hollow nanomaterial, wherein the preparation method comprises:

[0030] 0.1 g of cobalt-based binary transition metal glycerate complex and 0.15 g of thioacetamide were added to 60 mL of ethanol. The resulting suspension was transferred to a 100 mL high-pressure reactor and reacted at 160 °C for 12 h. After cooling, the mixture was centrifuged, washed, and dried to obtain a two-component multi-shell hollow sulfide nanomaterial, namely cobalt sulfide / cadmium sulfide two-component shell.

[0031] The cobalt-based binary transition metal glycerate complex is prepared by adding cobalt nitrate and cadmium nitrate in a molar ratio of 1:1 to a mixed solution of glycerol and isopropanol in a volume ratio of 1:4, stirring until homogeneous, and then transferring the mixture to a 100 mL high-pressure reactor and reacting at 180 °C for 6 h.

[0032] Example 2

[0033] The only difference between this embodiment and Embodiment 1 is that, in this embodiment, the metal salt is cobalt nitrate and lead nitrate, i.e., a cobalt sulfide / lead sulfide bicomponent shell.

[0034] Example 3

[0035] The only difference between this embodiment and Embodiment 1 is that, in this embodiment, the metal salt is cobalt nitrate and copper nitrate, i.e., a cobalt sulfide / copper sulfide bicomponent shell.

[0036] Example 4

[0037] The only difference between this embodiment and Embodiment 1 is that, in this embodiment, the vulcanization time is 6 hours.

[0038] Example 5

[0039] The only difference between this embodiment and Embodiment 1 is that, in this embodiment, the vulcanization time is 20 hours.

[0040] Test case

[0041] Morphological testing:

[0042] Transmission electron microscopy (TEM) was performed on the two-component multi-shell hollow sulfide nanomaterials prepared in Examples 1-5. The test results are as follows: Figure 1 and 2 As shown.

[0043] Performance testing:

[0044] The performance of the two-component multi-shell sulfide nanomaterials prepared in Examples 1, 4, and 5 was tested:

[0045] Photocatalytic water splitting for hydrogen production test:

[0046] The specific test method was as follows: 10 mg of sample was ultrasonically dispersed in 100 mL of an aqueous solution containing 10 vol% lactic acid. The suspension was then transferred to a reaction apparatus, and dissolved air in the suspension was removed using a vacuum pump. Visible light was used as the light source: a 300-watt xenon lamp equipped with a 420 nm cutoff filter. The reaction temperature was controlled at 10 °C using a constant-temperature circulating water pump. The emitted hydrogen gas was detected using a GC-7900 gas chromatograph at 30-minute intervals.

[0047] The test results are as follows:

[0048] (1) Figure 1 The images show transmission electron microscope (TEM) images of the products from Examples 1-3. As can be seen from the images, the bicomponent multi-shell hollow sulfide nanomaterials of the present invention all exhibit a multi-shell hollow structure.

[0049] (2) Figure 2The images are transmission electron microscope images of Examples 1, 4, and 5. As can be seen from the images, as the sulfidation reaction time increases, the crystallinity increases, the roughness of the shell increases, and the gaps between the shells become more obvious.

[0050] (3) Figure 3 The graph shows a comparison of the photocatalytic hydrogen production activities of the products from Examples 1, 4, and 5. It can be seen from the graph that the highest activity, reaching 16.94 mmol·g, was observed when the sulfidation reaction time was 12 h. -1 ·h -1 Neither too short nor too long a sulfidation reaction time can produce optimal photocatalytic activity.

[0051] The applicant declares that the detailed structural features of the present invention are illustrated through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the components selected in the present invention, additions of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0052] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0053] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

[0054] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. The application of two-component multi-shell sulfide hollow nanomaterials in photocatalysts for water splitting to produce hydrogen, characterized in that, The method for preparing the bicomponent multi-shell sulfide hollow nanomaterial includes: The bicomponent multi-shell sulfide hollow nanomaterial was prepared by sulfidation reaction of cobalt-based binary transition metal glycerate complex and sulfur source in an organic solvent. The sulfur source is selected from at least one of thioacetamide, thiourea, and L-cysteine; The mass ratio of the cobalt-based binary transition metal glycerate complex to the sulfur source is 1:1-4; The organic solvent is selected from at least one of methanol, ethanol, and isopropanol; The temperature of the sulfidation reaction is 120-200 ℃; The transition metal in the cobalt-based binary transition metal glycerate complex includes Co, and also includes one of Cd, Pb, and Cu.

2. The application according to claim 1, characterized in that, The preparation method of the two-component multi-shell sulfide hollow nanomaterial includes: Cobalt-based binary transition metal glycerate complexes were prepared by adding cobalt nitrate and cadmium nitrate in a molar ratio of 1:1 to a mixed solution of glycerol and isopropanol in a volume ratio of 1:4 and reacting the solutions with a solvothermal reaction.

3. The application according to claim 1, characterized in that, The concentration of the cobalt-based binary transition metal glycerate complex in the organic solvent is 0.001-0.01 g / mL.

4. The application according to claim 1, characterized in that, The vulcanization reaction takes 10 min to 20 h.

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