阅读说明：本技术 一种菱方相CuCrSe2纳米材料及其制备方法和应用 (Rhombohedral phase CuCrSe2Nano material and preparation method and application thereof ) 是由 王文亮 冯文玲 赵玉彤 刘燕 刘梦雪 于 2021-09-10 设计创作，主要内容包括：本发明公开一种菱方相CuCrSe-(2)纳米材料及其制备方法和应用。所述CuCrSe-(2)纳米材料的晶型为菱方相,其微观形貌为纳米级的盘状和/或多边形片状结构。所述制备方法包括步骤：(1)将含有可溶性铜源、铬源、硒源的高沸点反应介质进行溶剂热反应；(2)所述溶剂热反应完成后分离出其中的固体产物,去除其表面残留溶剂,即得。本发明的方法合成的菱方相CuCrSe-(2)纳米材料结晶度高、单分散性高、形貌尺寸均一,且具有圆盘状或多边形片状结构的形貌。本发明方法的反应条件温和、工艺简单,实现了尺寸可控、形貌均一、结晶度高、单分散的菱方相CuCrSe-(2)纳米材料的可控制备,这种纳米材料在光电子器件领域中具有广阔的应用前景。(The invention discloses rhombohedral phase CuCrSe 2 A nano material and a preparation method and application thereof. The CuCrSe 2 The crystal form of the nano material is rhombohedral phase, and the microscopic appearance of the nano material is a nano disc-shaped and/or polygonal sheet-shaped structure. The preparation method comprises the following steps: (1) carrying out solvothermal reaction on a high-boiling-point reaction medium containing a soluble copper source, a chromium source and a selenium source; (2) and separating a solid product from the solvent after the solvothermal reaction is finished, and removing the residual solvent on the surface of the solid product to obtain the catalyst. Rhombohedral phase CuCrSe synthesized by the method 2 The nanometer material has high crystallinity, high monodispersity, uniform appearance and size and the appearance of a disc-shaped or polygonal flaky structure. The method has mild reaction conditions and simple process, and realizes the monodisperse rhombohedral phase CuCrSe with controllable size, uniform appearance, high crystallinity 2 The controllable preparation of the nano material has wide application prospect in the field of photoelectronic devices.)

1. CuCrSe₂The nanometer material is characterized in that the crystal form of the nanometer material is rhombohedral phase, and the microscopic appearance of the nanometer material is a nanoscale disc-shaped and/or polygonal sheet-shaped structure.

2. The CuCrSe of claim 1₂Nanomaterial characterized in that the CuCrSe is₂The nano material is in a monodisperse state.

3. CuCrSe according to claim 1 or 2₂Nanomaterial characterized in that the CuCrSe is₂The diameter of the nano material is between 10 and 30nm, and the thickness of the nano material is between 5 and 15 nm.

4. Rhombohedral phase CuCrSe₂The preparation method of the nano material is characterized by comprising the following steps:

(1) carrying out solvothermal reaction on a reaction medium containing a soluble copper source, a chromium source and a selenium source;

(2) and separating a solid product from the solvent after the solvothermal reaction is finished, and removing the residual solvent on the surface of the solid product to obtain the catalyst.

5. The rhombohedral phase of CuCrSe of claim 4₂The preparation method of the nano material is characterized in that in the step (1), the molar ratio of Cu to Cr to Se in the reaction medium is 1:1: 2-4.

6. The rhombohedral phase of CuCrSe of claim 4₂The preparation method of the nano material is characterized in that in the step (1), the copper source is selected from one or more of copper acetylacetonate, cuprous chloride, cupric nitrate or cupric acetate;

or, in the step (1), the chromium source is selected from one or more of chromium acetylacetonate, chromium trichloride, chromium nitrate and chromium acetate;

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

7. The rhombohedral phase of CuCrSe of claim 4₂The preparation method of the nano material is characterized in that in the step (1), the reaction medium is selected from any one or more of organic amine, oleic acid and octadecene; preferably, the organic amine is selected from one or more of oleylamine, octadecylamine or hexadecylamine.

8. The rhombohedral phase of CuCrSe of claim 4₂The preparation method of the nano material is characterized in that in the step (1), under the conditions of oxygen isolation and magnetic stirring, the copper source, the chromium source and the selenium source are added into a reaction medium and then heated to 100-160 ℃ to react for 30-60 min.

9. The rhombohedral phase of CuCrSe of claim 4₂The preparation method of the nano material is characterized in that in the step (1), the temperature of solvothermal reaction is 260-300 ℃, and the reaction time is 5-120 min;

preferably, in the step (2), a solid product in the reaction solution is separated by centrifugation or filtration, and then the solid product is washed by cyclohexane and absolute ethyl alcohol in sequence to obtain the target product.

10. The CuCrSe of any one of claims 1 to 3₂Nanomaterial and/or rhombohedral phase CuCrSe obtained by the preparation method according to any one of claims 4 to 9₂The application of the nano material in the fields of thermoelectricity, photoelectricity or tumor diagnosis and treatment.

Technical Field

The invention belongs to CuCrSe₂The technical field of preparation, in particular to rhombohedral phase CuCrSe₂A 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.

The nano material is a comprehensive subject crossed by multiple subjects of chemistry, physics, biology and material science, and is the basis of the development of nano science and technology. Due to the unique size and shape effect, optical, electrical, magnetic and thermal properties, the functional nano material has wide research and application prospects in the research fields of energy, environment, biomedicine and the like.

CuCrSe₂As a multifunctional material which is potentially applied to the research fields of thermoelectricity, photoelectricity, tumor diagnosis and treatment and the like, the nano material draws wide attention to the research on a synthetic method and a structure-performance relation of the nano material. At present, there are general studiesPreparation of CuCrSe by high-temperature solid phase method₂The technology utilizes a high-temperature solid-phase reaction method to heat copper powder, chromium powder and selenium particles to 900-1000 ℃ for reaction for 7-14 days to obtain CuCrSe₂. However, high temperature solid phase reaction method for the synthesis of CuCrSe₂High energy consumption and long time are needed in the process, which is not beneficial to future CuCrSe₂And (5) industrial development. In addition, the products of high temperature solid phase reaction processes often exhibit the deficiencies of uncontrollable size and non-uniform morphology, which can also affect or limit CuCrSe₂The performance and the application development in micro-nano devices.

Disclosure of Invention

Aiming at the problems, the invention provides rhombohedral phase CuCrSe₂A nano material and a preparation method and application thereof. The method has mild reaction conditions and simple process, and realizes the monodisperse rhombohedral phase CuCrSe with controllable size, uniform appearance, high crystallinity₂Controllable preparation of nano material. In order to achieve the purpose, the invention discloses the following technical scheme:

in a first aspect of the invention, there is provided a CuCrSe₂The crystal form of the nano material is rhombohedral phase, and the micro appearance of the nano material is a nano disc-shaped and/or polygonal sheet-shaped structure.

Further, the CuCrSe₂The nano material is in a monodisperse state, namely, each disc-shaped structure is not connected with each other and is not stacked with each other.

Further, the CuCrSe₂The diameter of the nano material is about 10-30 nm, and the thickness is about 5-15 nm.

Compared with CuCrSe prepared by the traditional method₂Nano material, the rhombohedral phase CuCrSe of the invention₂The nano material has stronger absorption capacity in the visible light range, and the self-driven photoelectric detector constructed by the nano material has the advantages of high response speed and high stability.

In a second aspect of the invention, there is provided a rhombohedral phase of CuCrSe₂The preparation method of the nano material comprises the following steps:

(1) carrying out solvothermal reaction on a high-boiling-point reaction medium containing a soluble copper source, a chromium source and a selenium source;

(2) and separating a solid product from the solvent after the solvothermal reaction is finished, and removing the residual solvent on the surface of the solid product to obtain the catalyst.

Further, in the step (1), the molar ratio of Cu to Cr to Se in the reaction medium is 1:1: 2-4.

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

Further, in the step (1), the chromium source is selected from one or more of chromium acetylacetonate, chromium trichloride, chromium nitrate and chromium acetate.

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

Further, in the step (1), the high boiling point reaction medium is selected from any one or more of organic amine, oleic acid and octadecene. Optionally, the organic amine is selected from one or more of oleylamine, octadecylamine or hexadecylamine.

Further, in the step (1), under the conditions of oxygen isolation (such as in nitrogen or inert gas atmosphere) and magnetic stirring, the copper source, the chromium source and the selenium source are added into a reaction medium, and then the mixture is heated to 100-160 ℃ for reaction for 30-60 min, so that the copper source, the chromium source and the selenium source are dissolved, and oxygen, moisture and low-boiling-point impurities in a reaction system are removed.

Further, in the step (1), the temperature of the solvothermal reaction is kept between 260 and 300 ℃, and the reaction time is controlled between 5 and 120 min.

Further, in the step (2), a solid product in the reaction liquid is separated by adopting a centrifugal or filtering mode, and then the solid product is washed by cyclohexane and absolute ethyl alcohol in sequence to obtain the target product.

In a third aspect of the invention, there is provided the rhombohedral phase CuCrSe₂The nanometer material is applied in the fields of thermoelectricity, photoelectricity, tumor diagnosis and treatment and the like.

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

(1) rhombohedral phase CuCrSe synthesized by the method₂The nanometer material has high crystallinity, high monodispersity, uniform appearance and size and the appearance of a disc-shaped or polygonal flaky structure. CuCrSe of this structure₂Has excellent absorption capacity in the visible light range and uses CuCrSe₂The self-driven photoelectric detector constructed by the nano material has the advantages of high response speed and high stability, and the reasons are as follows: rhombohedral phase CuCrSe with high monodispersity and uniform appearance and size₂The nano material is easy to carry out micro-nano processing film formation on a device substrate in a spin coating or drop coating mode, and can be in close contact with the substrate to form good CuCrSe₂a/Si heterojunction. Meanwhile, due to rhombohedral phase CuCrSe₂The nano material has the advantages of high crystallinity and strong light absorption, so that electrons-holes generated under the illumination effect can be effectively separated by a built-in electric field formed by the heterojunction, and the photoresponse of the photoelectric detector is improved.

(2) Rhombohedral phase CuCrSe synthesized by the method₂Has magnetism, and can be used as a novel multifunctional diagnosis and treatment agent applied to the field of tumor treatment. The reason is that the rhombohedral phase CuCrSe₂The nano material has the capability of absorbing in a wide wavelength range from visible light to near infrared light, and copper ions contained in the material can react with H in a tumor microenvironment₂O₂Fenton-like reactions occur, so the rhombohedral phase of CuCrSe of the invention₂The nano material has the potential of photothermal therapy and chemodynamic therapy of tumors guided by magnetic resonance imaging, photoacoustic imaging and photothermal imaging multimodality imaging.

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 is an X-ray diffraction pattern (XRD) of the desired product of the first example.

FIG. 2 is a Transmission Electron Microscope (TEM) photograph of a target product of the first embodiment.

FIG. 3 is a diagram of the ultraviolet-visible near infrared absorption (UV-vis-NIR) spectrum of the target product of the first example.

FIG. 4 is an I-t curve of a self-driven photodetector constructed as the object of the first embodiment.

Fig. 5 is a hysteresis curve of the object product of the first embodiment.

FIG. 6 is an X-ray diffraction pattern (XRD) of the desired product of the second example.

FIG. 7 is a Transmission Electron Microscope (TEM) photograph of a target product of the third example.

FIG. 8 is a Transmission Electron Microscope (TEM) photograph of a target product of the fourth example.

FIG. 9 is an X-ray diffraction pattern (XRD) of the target product of the fifth example.

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

Rhombohedral phase CuCrSe₂The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.1mmol of copper acetylacetonate, 0.1mmol of chromium acetylacetonate, 0.2mmol of diphenyl 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 130 ℃ under the condition of magnetic stirring, preserving heat and reacting for 30min, and removing water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 280 ℃, preserving the temperature, reacting for 30min, cooling to room temperature after the reaction is finished, centrifugally separating a solid product in the reaction solution, and centrifugally washing the solid product for 3 times by using cyclohexane and absolute ethyl alcohol respectively to obtain a solid product, namely the target product.

Second embodiment

Rhombohedral phase CuCrSe₂The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.1mmol of cuprous chloride, 0.1mmol of chromium acetylacetonate, 0.2mmol of diphenyl diselenide and 6.0ml of an organic solvent (a mixed solvent of oleic acid and oleylamine in a volume ratio of 1: 5) 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, preserving heat and reacting for 30min, and removing water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 280 ℃, preserving the temperature, reacting for 30min, cooling to room temperature after the reaction is finished, centrifugally separating a solid product in the reaction solution, and centrifugally washing the solid product for 3 times by using cyclohexane and absolute ethyl alcohol respectively to obtain a solid product, namely the target product.

Third embodiment

Rhombohedral phase CuCrSe₂The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.1mmol of copper acetylacetonate, 0.1mmol of chromium acetylacetonate, 0.1mmol of dibenzyl diselenide and 6.0ml of an organic solvent (a mixed solvent of octadecene and oleylamine at a volume ratio of 1: 5) 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, preserving heat and reacting for 30min, and removing water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 280 ℃, preserving the temperature, reacting for 30min, cooling to room temperature after the reaction is finished, centrifugally separating a solid product in the reaction solution, and centrifugally washing the solid product for 3 times by using cyclohexane and absolute ethyl alcohol respectively to obtain a solid product, namely the target product.

Fourth embodiment

Rhombohedral phase CuCrSe₂The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.1mmol of copper acetylacetonate, 0.1mmol of chromium acetylacetonate, 0.2mmol of diphenyl diselenide and 6.0ml 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, preserving heat and reacting for 30min, and removing water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 280 ℃, preserving the temperature, reacting for 30min, cooling to room temperature after the reaction is finished, centrifugally separating a solid product in the reaction solution, and centrifugally washing the solid product for 3 times by using cyclohexane and absolute ethyl alcohol respectively to obtain a solid product, namely the target product.

Fifth embodiment

Rhombohedral phase CuCrSe₂The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.1mmol of copper acetylacetonate, 0.1mmol of chromium acetate, 0.2mmol of diphenyl diselenide and 6.0ml 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 100 ℃ under the condition of magnetic stirring, preserving the temperature and reacting for 60min, and removing water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 280 ℃, preserving the temperature, reacting for 30min, cooling to room temperature after the reaction is finished, centrifugally separating a solid product in the reaction solution, and centrifugally washing the solid product for 3 times by using cyclohexane and absolute ethyl alcohol respectively to obtain a solid product, namely the target product.

Sixth embodiment

Rhombohedral phase CuCrSe₂The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.1mmol of copper nitrate, 0.1mmol of chromium nitrate, 0.2mmol of selenium dioxide and 6.0ml 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 160 ℃ under the condition of magnetic stirring, preserving heat and reacting for 30min, and removing water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 300 ℃, preserving the heat, reacting for 5min, cooling to room temperature after the reaction is finished, centrifugally separating out a solid product in the reaction solution, and centrifugally washing the solid product for 3 times by using cyclohexane and absolute ethyl alcohol respectively to obtain a solid product, namely the target product.

Seventh embodiment

Rhombohedral phase CuCrSe₂The preparation of the nano material comprises the following steps:

(1) in a 100ml three-necked flask, 0.1mmol of copper acetate, 0.1mmol of chromium trichloride, 0.2mmol of selenium powder and 6.0ml of hexadecylamine 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 140 ℃ under the condition of magnetic stirring, preserving heat and reacting for 40min, and removing water and low-boiling-point impurities in the reaction system.

(3) And continuously heating the mixed solution to 260 ℃, preserving the temperature, reacting for 120min, cooling to room temperature after the reaction is finished, centrifugally separating out a solid product in the reaction solution, and centrifugally washing the solid product for 3 times by using cyclohexane and absolute ethyl alcohol respectively to obtain a solid product, namely the target product.

Eighth embodiment

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 well indexed CuCrSe₂(JCPDS Card number 73-2241) without other impurity peaks, which indicates that the target product prepared by the method of the embodiment is rhombohedral phase CuCrSe₂And (4) crystals. Similarly, the results in fig. 6 and 9 also show that the target products prepared by the second and fifth embodiments have the similar results to those in fig. 1.

FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the objective product obtained in the first example, showing that CuCrSe prepared by the method₂Is a disc-shaped or polygonal sheet-shaped nano material with a diameter of about 10-30 nm and a thickness of about 5-15 nm, and the obtained CuCrSe₂The size of the composite material is uniform and controllable. Similarly, the results in fig. 7 and 8 also show that the target products prepared by the third and fourth embodiments have the similar results to those in fig. 2.

FIG. 3 is a graph of the ultraviolet-visible near infrared absorption (UV-vis-NIR) spectrum of the product obtained in the first example demonstrating rhombohedral phase CuCrSe₂The nano material has stronger absorption in the visible-near infrared light range, which shows that the CuCrSe prepared by the method₂The nano material can be used as a photoelectric conversion material to be applied to the research field of photoelectric detectors.

FIG. 4 is an I-t curve of a self-driven photodetector constructed from the product obtained in the first embodiment, in which a target product obtained in the first embodiment and a graphene electrode are formed on a silicon wafer by a spin coating process to construct CuCrSe₂The result of the self-driven photodetector of the/Si heterostructure type is shown in fig. 4, and it can be seen that: the photoelectric detector has the advantages of good quick response and stability under the conditions of 650nm wavelength and external zero bias voltage.

FIG. 5 is a hysteresis curve of the target product obtained in the first example at 300K, showing that the rhombohedral phase CuCrSe prepared by the method₂The nano material has magnetism, and can be used as a novel multifunctional diagnosis and treatment agent to be applied to the field of tumor treatment.

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.