A multi-level structure CrSbSe3 nanomaterial and its preparation method and application

Abstract

The present invention discloses a multi-level structure CrSbSe3 nanomaterial, its preparation method and application. The microscopic morphology of the nanomaterial is a "flower-like" multi-level nanostructure formed by self-assembly of nanosheets, and the crystal form of the nanomaterial is an orthorhombic phase. The preparation method comprises the following steps: (1) selecting soluble substances of chromium, antimony and selenium as chromium source, antimony source and selenium source respectively. (2) adding the chromium source and antimony source to a reaction medium composed of organic amine, oleic acid and octadecene, heating and dissolving to obtain solution A. (3) heating and dissolving the selenium source in oleylamine to obtain solution B, and mixing solution A and solution B to carry out a solvent thermal reaction to obtain a multi-level structure CrSbSe3 nanomaterial. The method of the present invention has mild reaction conditions and simple process. The prepared CrSbSe3 is a multi-level nanostructure with high crystallinity and has excellent catalytic degradation ability of environmental pollutants.

Description

Technical Field

[0001] The present invention relates to the technical field of multi-level structure nanomaterials, and in particular to a multi-level structure CrSbSe3 nanomaterial, a preparation method of the nanomaterial and an application of the nanomaterial as a photocatalytic material. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

[0003] In the storage and conversion of clean renewable energy, the structure of catalyst materials is a key factor influencing catalytic performance. Among various nanostructures, hierarchical nanostructured materials are considered an ideal building block for enhancing catalytic performance and have garnered widespread attention. Among these, chromium-based bimetallic selenides, due to their diverse crystal structures and elemental compositions, have sparked significant research interest in catalysis, photoelectric conversion, environmental pollution purification, and information processing and storage.

[0004] CrSbSe3, a material with both ferromagnetic and semiconductor properties, has significant potential for applications in logic operations, information processing, and storage. Guy Ouvrard reported synthesizing CrSbSe3 through a high-temperature solid-phase reaction by mixing chromium powder, iron powder, and selenium powder in a ratio of 1:1:3, heating to 700°C, and reacting for five days. Furthermore, Xu Xiaohong and Mircea Dinca reported synthesizing one-dimensional CrSbSe3 nanostructures using template and exfoliation methods, respectively, and investigated their magnetic properties.

[0005] However, the above-mentioned high-temperature solid-phase reaction method not only requires high energy consumption and a long time in the preparation of CrSbSe3, but also the synthesized products usually exhibit the shortcomings of uncontrollable size and non-uniform morphology, which greatly affects or limits the performance and application of CrSbSe3. In addition, there are few reports on the preparation of multi-level structured CrSbSe3 nanomaterials and their performance research. The inventors believe that it is of great significance to explore CrSbSe3 nanomaterials with different structures and their applications in energy storage and conversion. Summary of the Invention

[0006] In response to this situation, the present invention aims to provide a multi-level CrSbSe nanomaterial. This solvothermal method produces a self-assembled, multi-level structure, which offers significant advantages as a photochemical energy conversion material. The present invention has demonstrated the application of this synthesized multi-level CrSbSe nanomaterial as a photocatalytic material. Results demonstrate that this multi-level CrSbSe nanomaterial can effectively photocatalytically degrade the environmental pollutant methylene blue.

[0007] Based on the above technical effects, the present invention provides the following technical solutions:

[0008] In a first aspect of the present invention, a multi-level structured CrSbSe3 nanomaterial is provided, wherein the crystal structure of the nanomaterial is an orthorhombic phase.

[0009] The nanomaterial is composed of several nanosheets self-assembled in a "flower-like" multi-level structure extending outward from the center of a sphere. Furthermore, the nanosheets have a thickness of 10-30 nm and a side length of 100-200 nm. The present invention prepares the nanomaterial via a solvothermal method. Based on the reaction medium provided by the present invention, similar effects can be achieved using different precursor sources. This method offers the advantages of good reproducibility, simplicity, and cost-effectiveness.

[0010] Therefore, the second aspect of the present invention provides a method for synthesizing the CrSbSe3 nanomaterial described in the first aspect, comprising the following steps:

[0011] A chromium source and an antimony source are added to a reaction medium consisting of an organic amine, oleic acid and octadecene, and heated to dissolve to obtain a solution A; a selenium source is heated to dissolve in oleylamine to obtain a solution B, and the solutions A and B are mixed to undergo a solvent thermal reaction to obtain the product.

[0012] In the above preparation method, the chromium source, antimony source and selenium source should be substances that can be dissolved in the reaction medium, including corresponding organic and inorganic substances, and the molar ratio of Cr:Sb:Se is preferably 1:1:3~6.

[0013] More preferably, the chromium source is selected from one or a combination of chromium trichloride, chromium acetylacetonate or chromium acetate; the antimony source is selected from one or a combination of triphenylantimony, antimony trichloride, antimony acetate or antimony bromide; and the selenium source is selected from one or more of diphenyl diselenide, dibenzyl diselenide, selenium dioxide or selenium powder.

[0014] In the above reaction medium, the organic amine is selected from one or more of oleylamine, hexadecylamine or octadecylamine, wherein the organic amine, oleic acid and octadecylene are mixed in a volume ratio of 5-8:1-2:1-3.

[0015] The preparation of the above-mentioned solution A is preferably carried out in a nitrogen or other inert gas atmosphere. After the chromium source and antimony source are added to the reaction medium, the reaction is heated to 100-180°C and reacted for 30-120 minutes with continuous stirring to dissolve the chromium source and antimony source and remove oxygen, moisture and low-boiling impurities in the reaction system.

[0016] In the preparation of the above-mentioned solution B, the preferred heating temperature is 70-250°C.

[0017] The solvothermal reaction parameters are as follows: the solution temperature is maintained between 280°C and 350°C, and the reaction time is controlled between 5 and 180 minutes. After the solvothermal reaction, the solid material in the reaction system is separated and retained, and then washed with an organic reagent to obtain the CrSbSe3 nanomaterial. This separation can be performed by centrifugation or filtration, and the organic reagent used for washing is anhydrous ethanol and / or cyclohexane.

[0018] This "flower-like" CrSbSe3 nanomaterial prepared by the above method has not been reported in existing research. Through electron microscopy observation, the CrSbSe3 nanomaterial presents multiple nanosheets extending arbitrarily outward from the center of the sphere. This structure has significant advantages as a catalytic material: the outward-extending sheet structure can capture, absorb irradiation from different directions, and reflect light, and has a better light absorption effect; the flower-like structure can provide a larger specific surface area and is not easy to stack or agglomerate; the intrinsic non-layered crystal structure provides more active sites for the catalytic reaction. The third aspect of the present invention provides the application of the CrSbSe3 nanomaterial described in the first aspect as a photocatalytic degradation of environmental pollutants.

[0019] The present invention uses the photodegradation of methylene blue as a model to verify the photocatalytic efficiency of the nanomaterial. Specifically, the nanomaterial is used as a photocatalytic degradation material to degrade dye pollutants in aquatic environments. The aquatic environment includes natural environments such as rivers, lakes, and oceans, as well as industrial and domestic water such as drinking water and treated sewage. The dye is a dye that can be degraded under light conditions, including but not limited to methylene blue, methylene blue, and Sudan red. In one embodiment verified by the present invention, the dye is methylene blue.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. The CrSbSe3 nanomaterial synthesized by the method of the present invention is an orthorhombic crystalline phase with high crystallinity and contains two-dimensional polygonal sheet nanostructures. Furthermore, the two-dimensional sheet-like CrSbSe3 nanomaterial can self-assemble into a "flower-like" multi-level nanostructure.

[0022] 2. The multi-level CrSbSe3 nanostructure can absorb scattered or reflected incident light multiple times in terms of solar energy storage and conversion, thereby improving the light absorption capacity of the material.

[0023] 3. The multi-level CrSbSe3 nanostructure can provide a larger specific surface area and accelerate the transmission of substances and electrons in the catalytic reaction process in the field of catalytic applications. On the other hand, it can overcome the shortcomings of stacking or agglomeration between catalysts.

[0024] 4. As an intrinsic non-layered crystal structure, the orthorhombic phase CrSbSe3 has a "flower-like" multi-level nanostructure morphology, which can provide abundant catalytic active sites due to the presence of dangling bonds on its surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The accompanying drawings, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0026] Figure 1 is the X-ray diffraction pattern (XRD) of the nanomaterial described in Example 1.

[0027] Figure 2 is a scanning electron microscope (SEM) photograph of the nanomaterial described in Example 1.

[0028] Figure 3 This is the ultraviolet-visible-near-infrared (UV-vis-NIR) absorption spectrum of the nanomaterial described in Example 1.

[0029] Figure 4 This is a graph showing the photocatalytic degradation of methylene blue by the nanomaterial described in Example 1.

[0030] Figure 5 is the X-ray diffraction pattern (XRD) of the nanomaterial described in Example 2.

[0031] Figure 6 is a scanning electron microscope (SEM) photograph of the nanomaterial described in Example 3.

[0032] Figure 7 is the X-ray diffraction pattern (XRD) of the nanomaterial described in Example 4. DETAILED DESCRIPTION

[0033] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs.

[0034] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0035] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0036] Example 1

[0037] A multi-level structure CrSbSe3 nanomaterial, the preparation method of which comprises the following steps:

[0038] (1) In a 100 ml three-necked flask, add 0.1 mmol of chromium acetylacetonate, 0.1 mmol of triphenylantimony, 8.0 ml of oleylamine, 1.0 ml of oleic acid, and 1.0 ml of octadecene. Then, introduce nitrogen and heat the mixture to 130°C under magnetic stirring for 60 min to obtain Solution A.

[0039] (2) In a 10 ml test tube, add 0.3 mmol of diphenyl diselenide and 1.0 ml of oleylamine, respectively. Dissolve diphenyl diselenide in oleylamine under ultrasonication and heating to 90 °C to obtain solution B.

[0040] (3) When solution A is heated to 320°C, 1.0 ml of solution B is quickly injected into solution A, and the reaction is continued at 320°C for 120 minutes. After the reaction is completed, the solution is cooled to room temperature. The solid product is then washed and centrifuged three times with a mixture of anhydrous ethanol and cyclohexane in a volume ratio of 3:1. The resulting solid product is the nanomaterial.

[0041] Example 2

[0042] A preparation method of a multi-level structured CrSbSe3 nanomaterial comprises the following steps:

[0043] (1) In a 100 ml three-necked flask, add 0.1 mmol of chromium acetylacetonate, 0.1 mmol of antimony acetate, 7.0 ml of oleylamine, 1.0 ml of oleic acid, and 2.0 ml of octadecene. Then, introduce nitrogen and heat the mixture to 160°C under magnetic stirring for 30 min to obtain Solution A.

[0044] (2) In a 10 ml test tube, add 0.3 mmol of diphenyl diselenide and 1.0 ml of oleylamine, respectively. Dissolve diphenyl diselenide in oleylamine under ultrasonication and heating to 90 °C to obtain solution B.

[0045] (3) When solution A is heated to 300°C, 1.0 ml of solution B is quickly injected into solution A and the reaction is continued at 300°C for 120 min. After the reaction is completed, the mixture is cooled to room temperature. The solid product is then washed and centrifuged three times with a mixture of anhydrous ethanol and cyclohexane in a volume ratio of 3:1. The resulting solid product is the target product.

[0046] Example 3

[0047] A preparation method of a multi-level structured CrSbSe3 nanomaterial comprises the following steps:

[0048] (1) In a 100 ml three-necked flask, add 0.1 mmol of chromium trichloride, 0.1 mmol of antimony acetate, 5.0 ml of oleylamine, 2.0 ml of oleic acid, and 3.0 ml of octadecene. Then, introduce nitrogen and heat the mixture to 160°C under magnetic stirring for 30 min to obtain Solution A.

[0049] (2) In a 100 ml three-necked flask, add 3 mmol of selenium powder and 10 ml of oleylamine, respectively. Ultrasonicate and then heat to 250 °C to dissolve the selenium powder in the oleylamine to obtain solution B.

[0050] (3) When solution A is heated to 350°C, 1.0 ml of solution B is quickly injected into solution A and the reaction is continued at 350°C for 30 min. After the reaction is completed, the mixture is cooled to room temperature. The solid product is then washed and centrifuged three times with a mixture of anhydrous ethanol and cyclohexane in a volume ratio of 3:1. The resulting solid product is the target product.

[0051] Example 4

[0052] A preparation method of a multi-level structured CrSbSe3 nanomaterial comprises the following steps:

[0053] (1) In a 100 ml three-necked flask, add 0.1 mmol of chromium acetate, 0.1 mmol of antimony acetate, 8.0 ml of oleylamine, 1.0 ml of oleic acid, and 1.0 ml of octadecene. Then, introduce nitrogen and heat the mixture to 110°C under magnetic stirring for 120 min to obtain Solution A.

[0054] (2) In a 10 ml test tube, add 0.3 mmol of dibenzyl diselenide and 1.0 ml of oleylamine, respectively. Dissolve diphenyl diselenide in oleylamine under ultrasonication and heating to 70 °C to obtain solution B.

[0055] (3) When solution A is heated to 290°C, 1.0 ml of solution B is quickly injected into solution A and the reaction is continued at 290°C for 180 min. After the reaction is completed, the mixture is cooled to room temperature. The solid product is then washed and centrifuged three times with a mixture of anhydrous ethanol and cyclohexane in a volume ratio of 3:1. The resulting solid product is the target product.

[0056] Morphological characterization

[0057] Figure 1 、 Figure 5 and Figure 7These are the X-ray diffraction results of the CrSbSe3 nanomaterials described in Example 1, Example 2 and Example 4, respectively. Figure 1 The diffraction peaks all indicate the corresponding crystal planes in CrSbSe3 (JCPDS Card No. 88-0566) very well, and no other impurity peaks appear, indicating that the nanomaterial prepared in Example 1 is an orthorhombic phase CrSbSe3 crystal. Figure 5 、 Figure 7 The results show that the nanomaterials prepared in Example 2 and Example 4 have substantially the same diffraction peaks as those in Example 1, proving that a CrSbSe3 crystal was obtained in all of the above examples.

[0058] Figure 2 and Figure 6 The following are scanning electron microscope (SEM) photos of the nanomaterials obtained in Example 1 and Example 3 respectively. Figure 2 It can be seen that the CrSbSe3 prepared in Example 1 is a nanomaterial with a sheet structure, with a thickness of about 10-30 nm and a side length of about 100-200 nm. Figure 6 The results also show that the nanomaterials prepared in Example 3 have Figure 2 Similar results were obtained. Figure 2 and Figure 6 The results also show that the nanomaterial provided by the present invention is a multi-level structure formed by self-assembly of several two-dimensional nanosheets. As shown in the figure, the multi-level structure refers to a multi-level structure similar to a "nanoflower" formed by cross-self-assembly of multiple sheets.

[0059] Performance Testing

[0060] Figure 3 This is the ultraviolet-visible-near-infrared (UV-vis-NIR) absorption spectrum of the nanomaterial in Example 1, which proves that the multi-level structure CrSbSe3 nanomaterial has strong absorption ability in the visible-near-infrared light range, indicating that the multi-level structure CrSbSe3 nanomaterial can be used as a light-absorbing material in research fields such as photocatalysis and photoelectric conversion.

[0061] Figure 4This is the result of the photocatalytic degradation of methylene blue by the nanomaterials described in Example 1. First, the multi-level structure CrSbSe3 nanomaterial was dispersed in a mixed solution of 4 mL of cyclohexane and 1 mL of mercaptopropionic acid under ultrasonic action, left to stand for 24 hours, and then washed three times by centrifugation with anhydrous ethanol for surface modification to enhance its water solubility. Secondly, 50 mg of the target product was weighed and dispersed into 50 mL of a 10 mg / L methylene blue aqueous solution, and stirred in the dark for 30 minutes to reach adsorption / desorption equilibrium. Then, a 300W xenon lamp was used for irradiation, and 1.0 mL of the mixed solution was centrifuged every 15 minutes. The supernatant was taken and the absorbance at a wavelength of 664 nm was measured using a UV-visible spectrophotometer to calculate the degradation rate. Figure 4 As shown, the hierarchical structured CrSbSe3 nanomaterials have good degradation ability for methylene blue dye.

[0062] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A multi-level CrSbSe3 nanomaterial with an orthorhombic crystal structure. The nanomaterial is composed of a plurality of nanosheets self-assembled in a "flower-like" multi-level structure extending outward from the center of a sphere. The thickness of the nanosheets is 10-30 nm and the side length is 100-200 nm.

2. The method for preparing the CrSbSe3 nanomaterial according to claim 1, characterized in that: The steps include: A chromium source and an antimony source are added to a reaction medium consisting of an organic amine, oleic acid and octadecene, and heated to dissolve to obtain a solution A; a selenium source is heated to dissolve in oleylamine to obtain a solution B, and the solutions A and B are mixed to undergo a solvent thermal reaction to obtain the product.

3. The preparation method according to claim 2, wherein The chromium source, antimony source and selenium source are substances that can be dissolved in the reaction medium, including corresponding organic and inorganic substances, and the molar ratio of Cr:Sb:Se is 1:1:3-6.

4. The preparation method according to claim 3, wherein The chromium source is selected from one or a combination of chromium trichloride, chromium acetylacetonate or chromium acetate; the antimony source is selected from one or a combination of triphenylantimony, antimony trichloride, antimony acetate or antimony bromide; and the selenium source is selected from one or more of diphenyl diselenide, dibenzyl diselenide, selenium dioxide or selenium powder.

5. The preparation method according to claim 2, wherein The organic amine is selected from one or more of oleylamine, hexadecylamine and octadecylamine, wherein the organic amine, oleic acid and octadecylene are mixed in a volume ratio of 5-8:1-2:1-3.

6. The preparation method according to claim 2, wherein The preparation of the solution A is carried out in a nitrogen or other inert gas atmosphere. After the chromium source and antimony source are added to the reaction medium, the reaction is heated to 100-180° C. and reacted for 30-120 minutes with continuous stirring to dissolve the chromium source and antimony source and remove oxygen, moisture and low-boiling-point impurities in the reaction system.

7. The preparation method according to claim 2, wherein In the preparation of the solution B, the heating temperature is 70-250°C.

8. The preparation method according to claim 2, wherein The parameters of the solvothermal reaction are as follows: the temperature of the solution is maintained between 280 and 350° C., and the reaction time is controlled between 5 and 180 minutes. After the solvothermal reaction is completed, the solid matter in the reaction system is separated and retained, and washed with an organic reagent to obtain the CrSbSe 3 nanomaterial.

9. Use of the CrSbSe3 nanomaterial according to claim 1 as a photocatalytic degradation material.

10. The use according to claim 9, characterized in that In the application, the nanomaterial is used as a photocatalytic degradation material to degrade dye pollutants in a water environment, the water environment includes a natural environment, and also includes industrial and domestic water, and the dye is selected from methyl blue, methylene blue or Sudan red.

11. The use according to claim 10, characterized in that The dye is methylene blue.

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