A hollow Cu3NbSe4 nanomaterial, its preparation method and application

Abstract

This invention belongs to the field of hollow multi-component nanomaterial preparation technology, specifically disclosing a hollow Cu3NbSe4 nanomaterial, its preparation method, and its application. The microstructure of the nanomaterial is a nanoscale hollow cubic structure. The preparation method includes: (1) dissolving niobium source and selenium source separately in oleylamine solvent by heating for later use; (2) treating the soluble copper source and the niobium source dissolved in (1) in a high-boiling-point organic solvent for deoxygenation and dehydration, and then carrying out a solvothermal reaction; (3) when (2) is heated to a certain temperature, injecting the selenium source dissolved in (1) to carry out a solvothermal reaction, and separating the obtained solid product after the reaction is completed. The synthesis process of this invention is simple, the reaction conditions are mild, and the energy consumption and cost are low; more importantly, it realizes the preparation of hollow Cu3NbSe4 nanomaterial with uniform morphology and size, high crystallinity, and stronger light absorption capacity, and the prepared hollow Cu3NbSe4 shows excellent performance in photocatalytic hydrogen production.

Description

Technical Field

[0001] This invention belongs to the field of hollow multi-component nanomaterial preparation technology, specifically relating to a hollow Cu3NbSe4 nanomaterial, its preparation method, and its application. Background Technology

[0002] Cu3NbSe4 materials, due to their suitable band structure, good charge transport characteristics, and high visible light absorption efficiency, have become potential candidates for energy conversion applications and have attracted widespread attention from researchers both domestically and internationally. Among them, patent CN113860270 A discloses a cubic phase Cu3NbSe4 nanomaterial and its preparation method, as well as its application in photodetectors.

[0003] In recent years, photocatalytic water splitting for hydrogen production and carbon dioxide reduction using solar energy has become a research hotspot. It is well known that the structure of catalyst materials is closely related to their performance. Therefore, optimizing the crystal structure and surface / interface structure of catalyst materials is an effective way to improve photocatalytic performance.

[0004] Hollow nanomaterials, due to their unique structure, possess properties such as low mass density, high specific surface area, strong light absorption, and short charge migration paths, making them promising candidates for applications in solar energy storage and conversion. Synthesis strategies for hollow nanomaterials can generally be categorized into three types: hard template methods, soft template methods, and self-templating methods. However, the differences in the reactivity of various reactants, as well as factors such as solvents, surface ligands, and reaction temperature, all affect the preparation of multi-component nanomaterials, making the synthesis of hollow Cu3NbSe4 nanostructures a significant challenge. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a hollow Cu3NbSe4 nanomaterial, its preparation method, and its applications. The synthesis process is simple, the reaction conditions are mild, energy consumption is low, and it is environmentally friendly. More importantly, it achieves the controllable preparation of hollow Cu3NbSe4 nanomaterials with uniform morphology, controllable size, and high crystallinity. The prepared hollow Cu3NbSe4 nanomaterials can be applied in the field of catalytic materials and have good catalytic effects. Specifically, the technical solution of this invention is as follows.

[0006] In a first aspect of the present invention, a hollow Cu3NbSe4 nanomaterial is provided, which has a hollow nanocube structure and also has the advantages of uniform morphology and size and high crystallinity.

[0007] Furthermore, the size of the hollow Cu3NbSe4 nanomaterial is 10~20 nm.

[0008] In a second aspect of the present invention, a method for preparing the hollow Cu3NbSe4 nanomaterial is provided, comprising the following steps:

[0009] (1) Niobium source and selenium source were dissolved in high-boiling-point organic solvents by heating to prepare niobium source solution and selenium source solution respectively;

[0010] (2) The copper source and the niobium source solution in step (1) are subjected to deoxygenation and dehydration treatment in a high-boiling-point organic solvent;

[0011] (3) Heat the reaction system in step (2) to a certain temperature, add the selenium source solution in step (1), and then heat to 260~320℃ for 5~120 min. After the reaction is completed, hollow Cu3NbSe4 nanomaterials are obtained.

[0012] Furthermore, the niobium source is niobium pentachloride and / or niobium oxalate; the selenium source is one or more of diphenyldiselenoether, selenium powder, dibenzyldiselenoether, and selenium dioxide; and the copper source is one or more of copper acetylacetonate, cuprous chloride, cuprous bromide, copper chloride, and copper acetate.

[0013] Furthermore, the high-boiling-point organic solvent is one or more of oleylamine, oleic acid, octadecene, hexadecylamine, and octadecylamine.

[0014] Further, the preparation method of the niobium source solution in step (1) is as follows: add the niobium source to a high-boiling-point organic solvent, and heat it to 150~210℃ for 30~120min under inert gas conditions to make it completely dissolved; the preparation method of the selenium source solution in step (1) is as follows: add the selenium source to a high-boiling-point organic solvent, and heat it to 70~210℃ for 30~120min under inert gas conditions to make it completely dissolved; the specific operation of dehydration and deoxygenation in step (2) is as follows: heat it to 100~160℃ for 30~90min under inert gas conditions.

[0015] Further, in step (3), when heated to 220°C, a selenium source solution is added and the reaction is kept at a constant temperature for 5-30 min. Then, the temperature is raised to 260-320°C and the reaction is continued for 5-120 min. When the reaction is completed and cooled to room temperature, the centrifuged solid product is washed with a mixture of anhydrous ethanol and cyclohexane to obtain hollow Cu3NbSe4 nanomaterials.

[0016] Furthermore, the molar ratio of Cu:Nb:Se in the reactants is 3:1:4~8.

[0017] In a second aspect of the invention, the hollow Cu3NbSe4 nanomaterial is provided for application in the fields of photocatalysis or optoelectronics, particularly in the field of photocatalytic hydrogen production, where it shows promising application prospects.

[0018] Compared with the prior art, the present invention has at least the following beneficial technical effects:

[0019] (1) The process for preparing hollow Cu3NbSe4 nanomaterials in this invention is simple, the reaction is mild, the energy consumption is low, and the environment is friendly. More importantly, it realizes the controllable preparation of hollow Cu3NbSe4 nanomaterials with uniform morphology and size, high crystallinity, and monodispersity.

[0020] (2) The hollow Cu3NbSe4 nanomaterial prepared by the present invention has a stronger absorption capacity in the visible light range, and the hollow Cu3NbSe4 nanomaterial has good photocatalytic performance as a photocatalyst. The reason is that the hollow structure can absorb the incident light that is scattered or reflected again, thereby improving the light absorption capacity of the material; larger specific surface area, abundant catalytic active sites and promote the transport of substances and electrons in the catalytic reaction. Attached Figure Description

[0021] The accompanying drawings, which form part of this specification, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. Hereinafter, embodiments of the invention will be described in detail with reference to the accompanying drawings, wherein:

[0022] Figure 1 This is the X-ray diffraction pattern (XRD) of the target product obtained in Example 1 of the present invention.

[0023] Figure 2 This is a transmission electron microscope (TEM) image of the target product obtained in Example 1 of the present invention;

[0024] Figure 3 This is the ultraviolet-visible (UV-vis) absorption spectrum of the target product obtained in Example 1 of the present invention;

[0025] Figure 4 This is the photocatalytic hydrogen production curve of the target product obtained in Example 1 of the present invention;

[0026] Figure 5 This is the X-ray diffraction pattern (XRD) of the target product obtained in Example 2 of the present invention.

[0027] Figure 6 This is a transmission electron microscope (TEM) image of the target product obtained in Example 3 of the present invention;

[0028] Figure 7 This is the X-ray diffraction pattern (XRD) of the target product obtained in Example 4 of the present invention.

[0029] Figure 8 This is a transmission electron microscope (TEM) image of the target product obtained in Example 5 of the present invention;

[0030] Figure 9 This is the X-ray diffraction pattern (XRD) of the target product obtained in Example 6 of the present invention. Detailed Implementation

[0031] The present invention is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of skill in the art. All reagents and materials used in this invention are readily available through conventional means, and unless otherwise specified, they shall be used in accordance with conventional methods in the art or as per the product instructions.

[0033] The present invention will now be further described in conjunction with the accompanying drawings and specific embodiments.

[0034] Example 1

[0035] Hollow Cu3NbSe4 nanomaterials were prepared by the following method:

[0036] (1) In a three-necked flask A, add 1 mmol of niobium pentachloride and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 180°C for 60 min under magnetic stirring to dissolve completely, to obtain a niobium pentachloride solution; In a three-necked flask B, add 4 mmol of diphenyldiselenoether and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 70°C for 30 min under magnetic stirring to dissolve completely, to obtain a diphenyldiselenoether solution;

[0037] (2) In a three-necked flask C, add 0.3 mmol of copper acetylacetone, 1 ml of niobium pentachloride solution in A and 8 ml of oleylamine, purge with nitrogen, and heat to 100 °C for 90 min under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0038] (3) Continue heating the mixture in C. When the temperature reaches 220℃, quickly inject 1 ml of diphenyl diselenide solution in B and react at a constant temperature for 30 min. Then continue heating to 280℃ and react at a constant temperature for 30 min. After the reaction is completed and naturally cooled to room temperature, add anhydrous ethanol and cyclohexane to wash and centrifuge the product 3 times to obtain the target product, namely hollow Cu3NbSe4 nanomaterial.

[0039] Example 2

[0040] Hollow Cu3NbSe4 nanomaterials were prepared by the following method:

[0041] (1) In a three-necked flask A, add 1 mmol of niobium pentachloride and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 210 °C for 30 min under magnetic stirring to dissolve completely, to obtain a niobium pentachloride solution; In a three-necked flask B, add 4 mmol of diphenyldiselenoether and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 70 °C for 30 min under magnetic stirring to dissolve completely, to obtain a diphenyldiselenoether solution;

[0042] (2) In a three-necked flask C, add 0.3 mmol of copper acetate, 1 ml of niobium pentachloride solution in A and 8 ml of oleylamine, purge with nitrogen, and heat to 160 °C for 30 min under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0043] (3) Continue heating the mixture in C. When the temperature reaches 220℃, quickly inject 1 ml of diphenyl diselenide solution in B and react at a constant temperature for 20 min. Then continue heating to 300℃ and react at a constant temperature for 10 min. After the reaction is completed and naturally cooled to room temperature, add anhydrous ethanol and cyclohexane to wash and centrifuge the product 3 times to obtain the target product, namely hollow Cu3NbSe4 nanomaterial.

[0044] Example 3

[0045] Hollow Cu3NbSe4 nanomaterials were prepared by the following method:

[0046] (1) In flask A, add 1 mmol of niobium pentachloride and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 210 °C for 30 min under magnetic stirring to dissolve completely, to obtain niobium pentachloride solution; In flask B, add 4 mmol of selenium powder and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 210 °C for 120 min under magnetic stirring to dissolve completely, to obtain selenium solution;

[0047] (2) In a three-necked flask C, add 0.3 mmol of cuprous chloride, 1 ml of niobium pentachloride solution in A, 7 ml of oleylamine and 1 ml of octadecene, purge with nitrogen, and heat to 130 °C for 60 min under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0048] (3) Continue heating the mixture in C. When the temperature reaches 220℃, quickly inject 1 ml of selenium solution in B and react at a constant temperature for 5 min. Then continue heating to 260℃ and react at a constant temperature for 120 min. After the reaction is completed and naturally cooled to room temperature, add anhydrous ethanol and cyclohexane to wash and centrifuge the product 3 times to obtain the target product, namely hollow Cu3NbSe4 nanomaterial.

[0049] Example 4

[0050] Hollow Cu3NbSe4 nanomaterials were prepared by the following method:

[0051] (1) In a three-necked flask A, add 1 mmol of niobium oxalate and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 150 °C for 60 min under magnetic stirring to dissolve completely, to obtain a niobium oxalate solution; In a three-necked flask B, add 4 mmol of dibenzyl diselenide and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 110 °C for 60 min under magnetic stirring to dissolve completely, to obtain a dibenzyl diselenide solution;

[0052] (2) In a three-necked flask C, add 0.3 mmol of copper acetylacetone, 1 ml of niobium oxalate solution in A and 8 ml of oleylamine, purge with nitrogen, and heat to 160 °C for 30 min under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0053] (3) Continue heating the mixture in C. When the temperature reaches 220℃, quickly inject 1 ml of dibenzyl diselenide solution in B and react at a constant temperature for 30 min. Then continue heating to 280℃ and react at a constant temperature for 30 min. After the reaction is completed and naturally cooled to room temperature, add anhydrous ethanol and cyclohexane to wash and centrifuge the product 3 times to obtain the target product, namely hollow Cu3NbSe4 nanomaterial.

[0054] Example 5

[0055] Hollow Cu3NbSe4 nanomaterials were prepared by the following method:

[0056] (1) In a three-necked flask A, add 1 mmol of niobium pentachloride and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 150 °C for 60 min under magnetic stirring to dissolve completely, to obtain a niobium pentachloride solution; In a three-necked flask B, add 4 mmol of diphenyldiselenoether and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 110 °C for 60 min under magnetic stirring to dissolve completely, to obtain a diphenyldiselenoether solution;

[0057] (2) In the three-necked flask C, add 0.3 mmol of copper acetylacetone, 1 ml of niobium pentachloride solution dissolved in A, 7 ml of oleylamine and 1 ml of oleic acid, purge with nitrogen, and heat to 160 °C for 30 min under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0058] (3) Continue heating the mixture in C. When the temperature reaches 220℃, quickly inject 1 ml of diphenyl diselenide solution in B and react at a constant temperature for 30 min. Then continue heating to 280℃ and react at a constant temperature for 30 min. After the reaction is completed and naturally cooled to room temperature, add anhydrous ethanol and cyclohexane to wash and centrifuge the product 3 times to obtain the target product, namely hollow Cu3NbSe4 nanomaterial.

[0059] Example 6

[0060] Hollow Cu3NbSe4 nanomaterials were prepared by the following method:

[0061] (1) In a three-necked flask A, add 1 mmol of niobium pentachloride and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 150 °C for 60 min under magnetic stirring to dissolve completely, to obtain a niobium pentachloride solution; In a three-necked flask B, add 4 mmol of diphenyldiselenoether and 10 ml of oleylamine, then purge with nitrogen gas, and heat to 110 °C for 60 min under magnetic stirring to dissolve completely, to obtain a diphenyldiselenoether solution;

[0062] (2) In a three-necked flask C, add 0.3 mmol of copper acetylacetone, 1 ml of niobium pentachloride solution in A, 7 ml of oleylamine and 1 ml of octadecylamine, purge with nitrogen, and heat to 160 °C for 30 min under magnetic stirring to remove water and low-boiling-point impurities from the reaction system.

[0063] (3) Continue heating the mixture in C. When the temperature reaches 220℃, quickly inject 1 ml of diphenyl diselenide solution in B and react at a constant temperature for 5 min. Then continue heating to 320℃ and react at a constant temperature for 5 min. After the reaction is completed and naturally cooled to room temperature, add anhydrous ethanol and cyclohexane to wash and centrifuge the product 3 times to obtain the target product, namely hollow Cu3NbSe4 nanomaterial.

[0064] Composition, structure characterization and performance testing

[0065] The X-ray diffraction pattern of the hollow Cu3NbSe4 nanomaterial prepared in Example 1 is shown below. Figure 1 As shown in the figure; it can be seen from the figure that the main diffraction peaks are located at 15.7°, 27.4°, 35.6°, 45.5°, 53.7°, 66.1° and 72.8°, which can all be identified as the corresponding (100), (111), (210), (220), (311), (400) and (331) crystal planes in Cu3NbSe4 (JCPDS Card No. 81-2492). No impurity peaks were found, proving that the product synthesized in this example is cubic phase Cu3NbSe4. The X-ray diffraction patterns of the hollow Cu3NbSe4 nanomaterials prepared in Examples 2, 4 and 6 are shown in the figure. Figure 5 , Figure 7 and Figure 9 As shown, similarly, Figure 5 , Figure 7 and Figure 9 The results also showed that the hollow Cu3NbSe4 nanomaterials prepared in Examples 2, 4 and 6 had similar results to those in Example 1.

[0066] Transmission electron microscopy (TEM) image of the hollow Cu3NbSe4 nanomaterials prepared in Example 1 is shown below. Figure 2 As shown, the Cu3NbSe4 prepared by the method of this application exhibits uniform morphology and size, displaying a hollow cubic structure with a size of 10-20 nm. Transmission electron microscopy (TEM) images of the hollow Cu3NbSe4 nanomaterials prepared in Examples 3 and 5 are shown below. Figure 6 and Figure 8 As shown; similarly, Figure 6 and Figure 8 The results also showed that the target products prepared in Examples 3 and 5 had similar results to those in Example 1. Furthermore, from... Figure 8 The observation of clear lattice fringes further proves that hollow Cu3NbSe4 has good crystallinity.

[0067] The UV-Vis absorption spectrum of the hollow Cu3NbSe4 nanomaterials prepared in Example 1 is shown below. Figure 3 As shown, hollow Cu3NbSe4 nanomaterials exhibit strong absorption in the visible light range, indicating that the hollow Cu3NbSe4 nanomaterials prepared by this method can be used as photocatalysts in the field of photocatalysis research.

[0068] Photocatalytic hydrogen production capacity test: First, the hollow Cu3NbSe4 nanomaterials prepared in Example 1 were dispersed in a mixture of 4 mL cyclohexane and 1 mL mercaptopropionic acid under ultrasonication, allowed to stand for 24 hours, and then washed three times with anhydrous ethanol by centrifugation to modify the surface and enhance its water solubility. Second, 50 mg of surface-modified hollow Cu3NbSe4 was weighed and dispersed in 100 mL of water. Third, the reaction was carried out in a relative vacuum system with an external glass reaction cell using a Labsolar-6A all-glass automated online micro-gas analysis system. The suspension was degassed in argon for 30 min to remove air from the reaction solution. Then, the reactor was vertically irradiated with a 300 W xenon lamp. During the reaction, the reactor was connected to a condenser to maintain the temperature of the reaction solution at around 5°C. During the photocatalytic water splitting process, the gaseous products were identified by gas chromatography. The photocatalytic hydrogen production results of the hollow Cu3NbSe4 nanomaterials prepared in Example 1 are shown in the figure below. Figure 4 As shown, hollow Cu3NbSe4 nanomaterials possess excellent photocatalytic hydrogen production capabilities.

[0069] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing hollow Cu3NbSe4 nanomaterials, characterized in that, Includes the following steps: (1) Niobium source and selenium source were dissolved in high-boiling-point organic solvents by heating to prepare niobium source solution and selenium source solution respectively; (2) The copper source and the niobium source solution in step (1) are subjected to deoxygenation and dehydration treatment in a high-boiling-point organic solvent; (3) Heat the reaction system in step (2) to a certain temperature, add the selenium source solution in step (1), and then heat to 260~320℃ for 5~120min. After the reaction is completed, hollow Cu3NbSe4 nanomaterials are obtained. In step (3), when heated to 220°C, a selenium source solution is added and the reaction is kept at a constant temperature for 5 to 30 minutes. Then, the temperature is raised to 260 to 320°C and the reaction is continued for 5 to 120 minutes. After the reaction is completed and cooled to room temperature, the centrifuged solid product is washed with a mixture of anhydrous ethanol and cyclohexane to obtain hollow Cu3NbSe4 nanomaterials. The molar ratio of Cu:Nb:Se in the reactants is 3:1:4 ~ 8.

2. The method for preparing hollow Cu3NbSe4 nanomaterials according to claim 1, characterized in that, The niobium source The source is niobium pentachloride and / or niobium oxalate; the selenium source is one or more of diphenyldiselenoether, selenium powder, dibenzyldiselenoether, and selenium dioxide; the copper source is one or more of copper acetylacetonate, cuprous chloride, cuprous bromide, copper chloride, and copper acetate.

3. The method for preparing hollow Cu3NbSe4 nanomaterials according to claim 1, characterized in that, The aforementioned high boiling point The organic solvent is one or more of oleylamine, oleic acid, octadecene, hexadecylamine, and octadecylamine.

4. The method for preparing hollow Cu3NbSe4 nanomaterials according to claim 1, characterized in that, The method for preparing the niobium source solution in step (1) is as follows: add the niobium source to a high-boiling-point organic solvent, and heat it to 150 ~ 210℃ for 30 ~ 120 min under inert gas conditions to make it completely dissolved; the method for preparing the selenium source solution in step (1) is as follows: add the selenium source to a high-boiling-point organic solvent, and heat it to 70 ~ 210℃ for 30 ~ 120 min under inert gas conditions to make it completely dissolved; the specific operation for removing water and oxygen in step (2) is as follows: heat it to 100 ~ 160℃ for 30 ~ 90 min under inert gas conditions.

5. A hollow Cu3NbSe4 nanomaterial prepared by the preparation method according to any one of claims 1 to 4, characterized in that, The hollow Cu3NbSe4 nanomaterial described herein has a hollow nanocubic structure.

6. The hollow Cu3NbSe4 nanomaterial according to claim 5, characterized in that, The hollow Cu3NbSe4 nanomaterial has a size of 10~20nm.

7. The application of hollow Cu3NbSe4 nanomaterials prepared by the preparation method according to any one of claims 1 to 4, or hollow Cu3NbSe4 nanomaterials according to any one of claims 5 to 6, in the fields of photocatalysis or optoelectronics.

8. The application according to claim 7, characterized in that, The hollow Cu3NbSe4 nanomaterial described above is applied in the field of photocatalytic hydrogen production.

Images