阅读说明：本技术 一种立方相Cu3NbSe4纳米材料及其制备方法和应用 (Cubic phase Cu3NbSe4Nano material and preparation method and application thereof ) 是由 王文亮 冯文玲 赵玉彤 张文骞 刘梦雪 于 2021-09-27 设计创作，主要内容包括：本发明属于Cu-(3)NbSe-(4)制备技术领域,具体公开一种立方相Cu-(3)NbSe-(4)纳米材料及其制备方法和应用。所述纳米材料的分子式为Cu-(3)NbSe-(4),其晶型为立方相,该纳米材料的微观形貌为纳米级的立方体结构。所述方法包括：(1)将含可溶性铜源、铌源、硒源的有机溶剂先进行除氧、除水处理,然后进行溶剂热反应；(2)分离出所述溶剂热反应得到的固体产物,即得。本发明的制备工艺更加简单、反应条件非常温和、能耗显著降低,而且成本低廉；更重要的是实现了形貌均一、尺寸可控、结晶度高,而且具有良好的单分散性的立方相Cu-(3)NbSe-(4)纳米材料的制备,因此,本发明制备的Cu-(3)NbSe-(4)在应用方面更易于进行微纳化和集成化加工。(The invention belongs to Cu 3 NbSe 4 The technical field of preparation, in particular to cubic phase Cu 3 NbSe 4 A nano material and a preparation method and application thereof. The molecular formula of the nano material is Cu 3 NbSe 4 The crystal form is cubic phase, and the micro appearance of the nano material is a nano cubic structure. The method comprises the following steps: (1) carrying out deoxidization and dehydration treatment on an organic solvent containing a soluble copper source, a niobium source and a selenium source, and then carrying out solvothermal reaction; (2) separating the solid obtained by the solvothermal reactionAnd (5) obtaining a product. The preparation process is simpler, the reaction condition is very mild, the energy consumption is obviously reduced, and the cost is low; more importantly, the cubic phase Cu with uniform appearance, controllable size, high crystallinity and good monodispersity is realized 3 NbSe 4 Preparation of nanomaterials, thus, Cu prepared by the invention 3 NbSe 4 The micro-nano and integrated processing is easier to carry out in the application aspect.)

1. Cu₃NbSe₄A nanomaterial characterized in that the nanomaterial has a molecular formula of Cu₃NbSe₄The crystal form is cubic phase; the micro appearance of the nano material is a nano-scale cube.

2. Cu according to claim 1₃NbSe₄Nanomaterial characterized in that the Cu₃NbSe₄The nano material is in a monodisperse state.

3. Cu according to claim 1 or 2₃NbSe₄Nanomaterial characterized in that the Cu₃NbSe₄The size of the nano material is 15-25 nm.

4. Cubic phase Cu₃NbSe₄The preparation method of the nano material is characterized by comprising the following steps:

(1) carrying out deoxidization and dehydration treatment on an organic solvent containing a soluble copper source, a niobium source and a selenium source, and then carrying out solvothermal reaction;

(2) and separating out a solid product obtained by the solvothermal reaction to obtain the catalyst.

5. Cubic phase Cu according to claim 4₃NbSe₄The preparation method of the nano material is characterized in that in the step (1), the ratio of Cu: nb: the molar ratio of Se is 3:1: 4-8 in sequence.

6. Cubic phase Cu according to claim 4₃NbSe₄The preparation method of the nano material is characterized in that in the step (1), the copper source is selected from one or more of cuprous chloride, cuprous bromide, copper acetylacetonate, cupric chloride or cupric acetate;

or, in the step (1), the niobium source is selected from one or two of niobium pentachloride and niobium oxalate;

or, in the step (1), the selenium source is selected from one or more of diphenyl diselenide, selenium powder, dibenzyl diselenide or selenium dioxide.

7. Cubic phase Cu according to claim 4₃NbSe₄The preparation method of the nano material is characterized in that in the step (1), the organic solvent is selected from organic amine; preferably, the organic amine is selected from one or more of oleylamine, hexadecylamine or octadecylamine.

8. Cubic phase Cu according to claim 4₃NbSe₄The preparation method of the nano material is characterized in that in the step (1), the copper source, the niobium source and the selenium source are added into a reaction medium under the condition of oxygen isolation, then are uniformly mixed, and then are heated to 100-150 ℃ to react for 30-60 min.

9. Cubic phase Cu according to claim 4₃NbSe₄The preparation method of the nano material is characterized in that in the step (1), the solvothermal temperature is kept between 270 and 310 ℃, and the reaction time is controlled between 5 and 120 min;

preferably, in the step (2), solid matters in the reaction solution are separated by centrifugation or filtration, and the centrifuged solid product is washed by a mixed solution of absolute ethyl alcohol and chloroform to obtain the target product.

10. Cu according to any of claims 1 to 3₃NbSe₄Nanomaterial and/or cubic phase Cu obtainable by the preparation process according to any one of claims 4 to 9₃NbSe₄The application of the nano material in the photovoltaic, thermoelectric or photoelectric field.

Technical Field

The invention belongs to Cu₃NbSe₄The technical field of preparation, in particular to cubic phase Cu₃NbSe₄A nano material and a preparation method and application thereof.

Background

The information in this background section is disclosed to enhance understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms part of the prior art already known to a person of ordinary skill in the art.

Solar energy has been considered by researchers as the first choice for replacing fossil energy as a clean and sustainable energy source. The functional nano material with photoelectric characteristics can convert optical signals into electric signals, and has wide application prospects in the fields of solar cells, photodetectors, biosensors, field effect transistors and the like.

The development of novel efficient nano photoelectric conversion materials becomes a hotspot of current research. Cu₃NbSe₄The nano material has a proper optical band gap and good charge transmission characteristics, has strong absorption in a visible light range, and has potential application prospects in the field of photoelectric conversion. At present, studies report that Cu can be prepared by heating copper powder, niobium powder and selenium powder to 573K for 24 hours by a solid-phase reaction method, then increasing the furnace temperature to 823K within 4 hours, keeping the temperature for 120 hours, and finally cooling to room temperature within 24 hours₃NbSe₄. However, the preparation method not only has long reaction time and high energy consumption, but also is more important for the product Cu₃NbSe₄The shape of the copper alloy is not uniform, the size is not controllable, and the copper alloy is not beneficial to Cu₃NbSe₄Large-scale production and micro-nano application.

Disclosure of Invention

In order to solve the above problems, the present invention provides a standCubic phase Cu₃NbSe₄A nano material and a preparation method and application thereof. Compared with the solid phase reaction method, the preparation process is simpler, the reaction condition is very mild, the energy consumption is obviously reduced, the cost is low, the method is environment-friendly, and more importantly, the cubic phase Cu with uniform appearance, controllable size and high crystallinity is realized₃NbSe₄And (4) preparing the nano material. In order to achieve the purpose, the invention discloses the following technical scheme:

in a first aspect of the present invention, there is provided Cu₃NbSe₄Nanomaterial with molecular formula of Cu₃NbSe₄The crystal form is cubic phase, and the microscopic appearance of the nano material is a nano-scale cubic structure. Relative to Cu prepared by solid-phase reaction method₃NbSe₄Material, cubic phase Cu of the invention₃NbSe₄The nano material not only has uniform appearance and controllable size, but also has good monodispersity and high crystallinity, so that the nano material is easier to carry out micro-nano and integrated processing in practical application.

Further, the Cu₃NbSe₄The nano material can show good dispersibility in a solvent, is in a monodisperse state and has good stability. Preparation of Cu by high temperature solid phase reaction₃NbSe₄The process of (2) is easy to generate sintering phenomenon, namely products are agglomerated together, and the dispersibility is poor.

Further, the Cu₃NbSe₄The size of the nano material is about 15-25 nm.

To this end, in a second aspect of the invention, a cubic phase Cu is provided₃NbSe₄The preparation method of the nano material comprises the following steps:

(1) carrying out deoxidization and dehydration treatment on an organic solvent containing a soluble copper source, a niobium source and a selenium source, and then carrying out solvothermal reaction;

(2) and separating out a solid product obtained by the solvothermal reaction to obtain the catalyst.

Further, in the step (1), the ratio of Cu: nb: the molar ratio of Se is 3:1: 4-8 in sequence.

Further, in the step (1), the copper source is selected from one or more of cuprous chloride, cuprous bromide, copper acetylacetonate, cupric chloride or cupric acetate.

Further, in the step (1), the niobium source is selected from one or two of niobium pentachloride and niobium oxalate.

Further, in the step (1), the selenium source is selected from one or more of diphenyl diselenide, selenium powder, dibenzyl diselenide or selenium dioxide.

Further, in the step (1), the organic solvent is selected from organic amines. Optionally, the organic amine is selected from one or more of oleylamine, hexadecylamine or octadecylamine. When the organic solvents are used as reaction media, the temperature required by the reaction can be met, and the organic solvents have the function of a surfactant, so that the morphology and the size of a product can be conveniently regulated and controlled.

Further, in the step (1), under an oxygen isolation condition (such as in a nitrogen or inert gas atmosphere), adding the copper source, the niobium source and the selenium source into a reaction medium, uniformly mixing, heating to 100-150 ℃, and reacting for 30-60 min to dissolve the copper source, the niobium source and the selenium source and remove moisture, oxygen and low-boiling-point impurities in the reaction system.

Further, in the step (1), the temperature of the solvothermal reaction is kept between 270 and 310 ℃, and the reaction time is controlled between 5 and 120 min. The target product is difficult to obtain when the reaction temperature is too low, and the function of the surfactant is easily inactivated and volatilized when the temperature is too high.

Further, in the step (2), solid matters in the reaction liquid are separated in a centrifugal or filtering mode, and the centrifugal solid products are washed by a mixed liquid of absolute ethyl alcohol and chloroform to obtain the target products.

In a third aspect of the present invention, there is provided the cubic phase Cu₃NbSe₄The application of the nano material in the fields of photoelectricity, thermoelectricity and the like.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

(1) compared with the solid-phase reaction method, the preparation process is simpler,The method has the advantages of very mild reaction conditions, obviously reduced energy consumption, low cost, environmental friendliness, and more importantly, the method realizes the cubic phase Cu with uniform appearance, controllable size, high crystallinity and good monodispersity₃NbSe₄Preparation of nanomaterials, thus, Cu prepared by the invention₃NbSe₄The micro-nano and integrated processing is easier to carry out in the application aspect. Because sintering phenomenon is easy to occur in the high-temperature solid-phase reaction process, namely products are agglomerated together, and the dispersibility is poor. The method is liquid phase preparation, reactants are dissolved in a solvent and then react in an ion or molecular form, and the reactants have the functions of a surfactant (such as crystal face selective adsorption and limitation of further growth of crystals) in the crystal nucleation and growth processes, so that the liquid phase reaction is obviously superior to the high-temperature solid phase reaction in the aspect of controlling the appearance and the size of a product.

(2) The research shows that the Cu prepared by the embodiment of the invention₃NbSe₄Has strong absorption capacity in the visible light range and uses Cu₃NbSe₄The photoelectric detector constructed by the nano material has the advantages of high response speed and high stability, and the reasons are as follows: cu with high monodispersity and uniform appearance and size₃NbSe₄The nano material can not only carry out micro-nano processing film formation on a device substrate (taking a monocrystalline silicon substrate as an example) in a spin coating or drop coating mode, but also can be in close contact with the substrate to form good Cu₃NbSe₄a/Si heterojunction. Furthermore, since Cu₃NbSe₄The nano material has the advantages of high crystallinity and strong light absorption, so the nano material is prepared in Cu₃NbSe₄Under the action of a built-in electric field formed by the/Si heterojunction, the effective separation of photo-generated electrons and holes can be promoted, and the performance of the photoelectric detector is improved.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:

FIG. 1 shows an X-ray diffraction pattern (XRD) of a target product obtained in accordance with a first embodiment of the present invention.

FIG. 2 is a Transmission Electron Microscope (TEM) photograph of a target product obtained in the first example of the present invention.

FIG. 3 is a diagram showing the ultraviolet-visible (UV-vis) absorption spectrum of the objective product obtained in the first example of the present invention.

FIG. 4 is an I-t curve of a photodetector constructed by the target product obtained in the first embodiment of the present invention. .

FIG. 5 is an X-ray diffraction pattern (XRD) of the object obtained in the second example of the present invention.

FIG. 6 is a Transmission Electron Microscope (TEM) photograph of a target product obtained by the third example of the present invention.

FIG. 7 is an X-ray diffraction pattern (XRD) of the object obtained in the fourth example of the present invention.

FIG. 8 is a Transmission Electron Microscope (TEM) photograph of a target product obtained in the fifth example of the present invention.

FIG. 9 shows the X-ray diffraction pattern (XRD) of the object obtained in the sixth example of the present invention.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications.

In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described in this invention are exemplary only. The invention will now be further described with reference to the drawings and specific examples in the specification.

First embodiment

Cubic phase Cu₃NbSe₄The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.3mmol cuprous chloride, 0.1mmol niobium pentachloride, 0.4mmol diphenyl diselenide and 6.0ml oleylamine were added, respectively, to obtain a mixed solution.

(2) And (2) introducing nitrogen into the three-mouth bottle in the step (1), heating the mixed solution to 130 ℃ under the condition of magnetic stirring, and carrying out heat preservation reaction for 30min to remove water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 280 ℃, preserving the heat, reacting for 30min, cooling to room temperature after the reaction is finished, and then washing and centrifuging the solid product for 3 times by using the mixed solution of absolute ethyl alcohol and chloroform with the volume ratio of 3:1 to obtain the solid product, namely the target product.

Second embodiment

Cubic phase Cu₃NbSe₄The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.3mmol of cuprous bromide, 0.1mmol of niobium oxalate, 0.4mmol of diphenyl diselenide and 5.0g of octadecylamine were added, respectively, to obtain a mixed solution.

(2) And (2) introducing nitrogen into the three-mouth bottle in the step (1), heating the mixed solution to 130 ℃ under the condition of magnetic stirring, and carrying out heat preservation reaction for 60min to remove water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 280 ℃, preserving the heat, reacting for 30min, cooling to room temperature after the reaction is finished, and then washing and centrifuging the solid product for 3 times by using the mixed solution of absolute ethyl alcohol and chloroform with the volume ratio of 3:1 to obtain the solid product, namely the target product.

Third embodiment

Cubic phase Cu₃NbSe₄The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.3mmol of cuprous chloride, 0.1mmol of niobium pentachloride, 0.4mmol of diphenyl diselenide and 4.5g of hexadecylamine were added, respectively, to obtain a mixed solution.

(2) And (2) introducing nitrogen into the three-mouth bottle in the step (1), heating the mixed solution to 100 ℃ under the condition of magnetic stirring, and carrying out heat preservation reaction for 60min to remove water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 270 ℃, preserving the temperature, reacting for 120min, cooling to room temperature after the reaction is finished, and then washing and centrifuging the solid product for 3 times by using the mixed solution of absolute ethyl alcohol and chloroform with the volume ratio of 3:1 to obtain the solid product, namely the target product.

Fourth embodiment

Cubic phase Cu₃NbSe₄The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.3mmol of copper acetylacetonate, 0.1mmol of niobium pentachloride, 0.4mmol of dibenzyl diselenide and 6.0ml of oleylamine were added, respectively, to obtain a mixed solution.

(2) And (2) introducing nitrogen into the three-mouth bottle in the step (1), heating the mixed solution to 120 ℃ under the condition of magnetic stirring, and carrying out heat preservation reaction for 45min to remove water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 310 ℃, preserving the heat, reacting for 5min, cooling to room temperature after the reaction is finished, and then washing and centrifuging the solid product for 3 times by using the mixed solution of absolute ethyl alcohol and chloroform with the volume ratio of 3:1 to obtain the solid product, namely the target product.

Fifth embodiment

Cubic phase Cu₃NbSe₄The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.3mmol of cuprous chloride, 0.1mmol of niobium pentachloride, 0.4mmol of diphenyl diselenide and 5.0g of octadecylamine were added, respectively, to obtain a mixed solution.

(2) And (2) introducing nitrogen into the three-mouth bottle in the step (1), heating the mixed solution to 150 ℃ under the condition of magnetic stirring, and carrying out heat preservation reaction for 20min to remove water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 280 ℃, preserving the heat, reacting for 30min, cooling to room temperature after the reaction is finished, and then washing and centrifuging the solid product for 3 times by using the mixed solution of absolute ethyl alcohol and chloroform with the volume ratio of 3:1 to obtain the solid product, namely the target product.

Sixth embodiment

Cubic phase Cu₃NbSe₄The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.3mmol of copper chloride, 0.1mmol of niobium pentachloride, 0.4mmol of selenium powder and 6.0ml of oleylamine are respectively added to obtain a mixed solution.

(2) And (2) introducing nitrogen into the three-mouth bottle in the step (1), heating the mixed solution to 100 ℃ under the condition of magnetic stirring, and carrying out heat preservation reaction for 60min to remove water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 300 ℃, preserving the heat, reacting for 30min, cooling to room temperature after the reaction is finished, and then washing and centrifuging the solid product for 3 times by using the mixed solution of absolute ethyl alcohol and chloroform with the volume ratio of 3:1 to obtain the solid product, namely the target product.

Seventh embodiment

Cubic phase Cu₃NbSe₄The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.3mmol of copper acetate, 0.1mmol of niobium pentachloride, 0.4mmol of selenium dioxide and 6.0ml of oleylamine were added, respectively, to obtain a mixed solution.

(2) And (2) introducing nitrogen into the three-mouth bottle in the step (1), heating the mixed solution to 140 ℃ under the condition of magnetic stirring, and carrying out heat preservation reaction for 30min to remove water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 290 ℃, preserving the heat, reacting for 60min, cooling to room temperature after the reaction is finished, and then washing and centrifuging the solid product for 3 times by using the mixed solution of absolute ethyl alcohol and chloroform with the volume ratio of 3:1 to obtain the solid product, namely the target product.

Composition, structural characterization and performance testing

FIG. 1 shows the X-ray diffraction pattern of the object obtained in the first example. As can be seen from the figure: all diffraction peaks are good indexes of Cu₃NbSe₄ (JCPDS Card number 81-2492) and no impurity peak appears, which indicates that the target product prepared by the method of the embodiment is cubic phase Cu₃NbSe₄And (4) crystals. Likewise, the results of fig. 5, 7 and 9 also show that the target products prepared by the second, fourth and sixth examples have similar results to fig. 1.

FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the objective product obtained in the first example, showing that Cu was prepared by the method₃NbSe₄The shape is uniform, the size is controllable, and the nano-cubic structure is embodied in a size of 15-25 nm. Similarly, the results of fig. 6 and 8 also show that the target products prepared by the third and fifth examples have similar results to those of fig. 2.

FIG. 3 is a ultraviolet-visible (UV-vis) absorption spectrum of the product obtained in the first example, demonstrating cubic phase Cu₃NbSe₄The nano material has stronger absorption in the visible light range, which shows that the Cu prepared by the method₃NbSe₄The nano material can be used as a photoelectric conversion material and applied to the research field of photoelectric equipment.

FIG. 4 is an I-t curve of a photodetector constructed by the product obtained in the first embodiment. In this experiment, the target product obtained in the first example and the graphene electrode were formed on a single crystal silicon wafer by a spin coating process to form Cu₃NbSe₄A photodetector of the/Si heterostructure type. As shown in fig. 4: the light intensity is 60mW/cm at the wavelength of 520nm²And the condition of applying 0.5V bias voltage shows that the photoelectric detector has good responsiveness and stability.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.