阅读说明：本技术 一种二维非层状CuGaSe2多孔纳米材料及其制备方法和应用 (Two-dimensional non-layered CuGaSe2Porous nano material and preparation method and application thereof ) 是由 王文亮 冯文玲 王卫华 赵玉彤 张文骞 刘梦雪 于 2021-09-17 设计创作，主要内容包括：本发明公开一种二维非层状CuGaSe-(2)多孔纳米材料及其制备方法和应用。该纳米材料的微观形貌为纳米级多孔片状结构,且该纳米材料的晶型为四方相。所述制备方法包括步骤：(1)将铜源溶于有机胺、油酸和十八烯构成的反应介质中,得A溶液。(2)将溶有硒源的十八烯溶液加入预热的所述A溶液中,得B溶液。(3)在所述B溶液进行溶剂热反应的过程中加入溶有镓源的油胺溶液,继续进行溶剂热反应,完成后分离出固体产物,即得二维非层状CuGaSe-(2)多孔纳米材料。相对于现有的纳米颗粒形态的CuGaSe-(2),本发明方法制备的CuGaSe-(2)材料为高结晶度的二维非层状多孔纳米材料,具有优异的环境污染物降解能力。(The invention discloses two-dimensional non-layered CuGaSe 2 Porous nano material and preparation method and application thereof. The microscopic appearance of the nano material is a nano-scale porous sheet structure, and the crystal form of the nano material is a tetragonal phase. The preparation method comprises the following steps: (1) dissolving a copper source in a reaction medium consisting of organic amine, oleic acid and octadecene to obtain a solution A. (2) And adding the octadecylene solution dissolved with the selenium source into the preheated solution A to obtain a solution B. (3) Adding oleylamine solution dissolved with gallium source in the process of carrying out solvothermal reaction on the solution B, continuously carrying out solvothermal reaction, and separating out a solid product after the solvothermal reaction is finished to obtain the two-dimensional non-lamellar CuGaSe 2 A porous nanomaterial. CuGaSe relative to existing nanoparticle morphology 2 CuGaSe prepared by the method of the invention 2 The material is a two-dimensional non-layered porous nano material with high crystallinity, and has excellent environmental pollutant degradation capability.)

1. CuGaSe₂The nanometer material is characterized in that the microscopic appearance of the nanometer material is a nanometer porous sheet structure, and the crystal form of the nanometer material is a tetragonal phase.

2. The CuGaSe of claim 1₂The nano material is characterized in that the thickness of the porous sheet structure is about 10-50 nm;

or the length of the porous sheet structure is about 0.2-1.5 mu m;

or the pore diameter of the porous sheet structure is about 2-80 nm.

3. CuGaSe₂Nanomaterial characterized in that the CuGaSe is₂The nano material is a plurality of pieces of CuGaSe as claimed in claim 1 or 2₂The nano material is self-assembled to form a multi-level structure material, and the multi-level structure is formed by the cross self-assembly of porous sheets.

4. Two-dimensional non-layered CuGaSe₂The preparation method of the porous nano material is characterized by comprising the following steps:

(1) dissolving a copper source in a reaction medium consisting of organic amine, oleic acid and octadecene to obtain a solution A;

(2) adding an octadecylene solution dissolved with a selenium source into the preheated solution A to obtain a solution B;

(3) adding oleylamine solution dissolved with gallium source in the process of carrying out solvothermal reaction on the solution B, continuously carrying out solvothermal reaction, and separating out a solid product after the solvothermal reaction is finished to obtain the two-dimensional non-lamellar CuGaSe₂A porous nanomaterial.

5. The two-dimensional non-layered CuGaSe of claim 4₂The preparation method of the porous nano material is characterized in that in the step (1), under the condition of oxygen isolation (preferably in nitrogen or inert gas atmosphere) and stirring, the copper source is added into a reaction medium composed of organic amine, oleic acid and octadecene, and then the mixture is heated to 100-180 ℃ for heat preservation;

preferably, the copper source is selected from one or more of cuprous chloride, cuprous bromide, cupric acetylacetonate or cupric acetate;

preferably, in the step (1), the organic amine, the oleic acid and the octadecene are sequentially mixed according to a molar ratio of 1: 3-8: 30; more preferably, the organic amine is selected from at least one of oleylamine, octadecylamine or hexadecylamine.

6. The two-dimensional non-layered CuGaSe of claim 4₂The preparation method of the porous nano material is characterized in that in the step (2), the selenium source is added into octadecene and heated to 80-200 ℃ and then is kept warm until the selenium source is fully dissolved;

preferably, the selenium source is selected from one or more of diphenyl diselenide, dibenzyl diselenide, selenium powder and selenium dioxide;

preferably, in the step (2), the temperature of the preheated solution A is 210-230 ℃.

7. The two-dimensional non-layered CuGaSe of claim 4₂The preparation method of the porous nano material is characterized in thatAdding the gallium source into oleylamine, heating to 100-160 ℃, and keeping the temperature; preferably, the gallium source is selected from one or more of gallium acetylacetonate, gallium tribromide and gallium trichloride;

preferably, the copper source, the gallium source and the selenium source are added according to the molar ratio of Cu to Ga to Se of 1:1: 2-4.

8. The two-dimensional non-layered CuGaSe of claim 4₂The preparation method of the porous nano material is characterized in that in the step (3), the temperature of the solvothermal reaction of the solution B is 210-230 ℃, and the reaction time is 5-30 min;

preferably, in the step (3), the temperature for continuously carrying out the solvothermal reaction is 220-260 ℃, and the reaction time is 10-120 min;

preferably, in the step (3), a solid product in the reaction solution is separated by centrifugation or filtration, and then the solid product is washed by absolute ethyl alcohol and cyclohexane in sequence to obtain the two-dimensional non-lamellar CuGaSe₂A porous nanomaterial.

9. The CuGaSe of any of claims 1-3₂Nanomaterial or two-dimensional non-layered CuGaSe according to any of claims 4 to 8₂The application of the porous nano material in the field of photocatalysis.

10. Use according to claim 9, wherein the two-dimensional non-layered CuGaSe is applied₂The porous nano material is used for photocatalytic degradation of organic pollutants and heavy metal ions in water.

Technical Field

The invention belongs to the technical field of preparation of functional nano materials, and particularly relates to two-dimensional non-layered CuGaSe₂Porous nano material and its preparation method and application.

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.

In recent years, the problem of environmental pollution has posed a serious threat to human health and ecosystem due to rapid development of industrialization and modernization, and thus, restoration of environmental pollution is imminent. In the research on the degradation of various environmental pollutants, the photocatalytic technology is considered to be one of the most promising technologies, and the design and development of novel efficient photocatalysts attract extensive attention at home and abroad.

The energy band structure and the shape and the size of the photocatalytic material are important factors influencing the photocatalytic performance. The band structure of the semiconductor material not only determines the redox capability of the catalyst, but also affects the photoresponse range of the catalyst. CuGaSe₂The nanometer material has ideal forbidden band width, high light absorption coefficient and carrier mobility and is used for sunlight absorptionThe method is widely applied to the research fields of solar cells, photoelectric detectors and the like, and the exploration of the synthesis method and the structure-performance relationship becomes the hot point of the current research.

Broadening the spectral response range and improving the separation efficiency of photon-generated carriers are effective ways to enhance the photocatalytic performance of semiconductors. The photocatalytic reaction mainly occurs on the surface of the catalyst, so the shape and size of the catalyst have great influence on the catalytic performance. Generally, the larger the specific surface area of the catalyst, the better the adsorption performance; the more active sites exposed, the better the catalytic performance. Researches find that the porous two-dimensional material has the advantages of both the two-dimensional material and the porous material, can provide larger effective specific surface area and rich active sites, and can accelerate mass transfer and electron transfer in the catalytic reaction process.

At present, most of the synthetic CuGaSe have been reported₂The morphology of the nano particles is mainly used, and researches show that the porous two-dimensional nano structure has the advantages of stronger light absorption capacity, more catalytic active sites and the like compared with the nano particles. However, since CuGaSe₂The characteristics of tetragonal crystal phase per se, CuGaSe is difficult to realize by the conventional synthesis method₂And (3) controllable preparation of the porous two-dimensional structure.

Disclosure of Invention

Aiming at the problems, the invention provides two-dimensional non-layered CuGaSe₂Porous nano material and its preparation method and application. CuGaSe relative to existing nanoparticle morphology₂CuGaSe prepared by the method of the invention₂The material is a two-dimensional non-layered porous nano material with high crystallinity, and has excellent environmental pollutant degradation capability. In order to achieve the purpose, the invention discloses the following technical scheme:

in a first aspect of the invention, there is provided a CuGaSe₂The nano material has a nano-scale porous sheet structure in the microscopic appearance, and the crystal form of the nano material is tetragonal phase, namely the nano material is a two-dimensional non-laminar material, namely CuGaSe with the characteristics₂The nanomaterial is hereinafter referred to as: two-dimensional non-laminar CuGaSe₂A porous nanomaterial.

Further, the thickness of the porous sheet structure is about 10-50 nm.

Further, the length of the porous sheet-like structure is about 0.2-1.5 μm.

Furthermore, the pore diameter of the porous sheet structure is about 2-80 nm.

Further, another micro-morphology of CuGaSe₂The porous nano material is as follows: several pieces of the two-dimensional non-layered CuGaSe₂The porous nanometer material is self-assembled to form the multilevel structural material.

Unlike two-dimensional layered materials, all atoms in the crystal of two-dimensional non-layered materials are chemically bonded, i.e., van der waals forces between layers of layered materials are not present. Due to the existence of isotropic chemical bonds, two-dimensional non-layered materials usually exhibit specific three-dimensional morphology to reduce internal energy and maintain stability of crystal structure, which is one of the key factors hindering the preparation of two-dimensional non-layered materials. At present, the preparation of two-dimensional non-layered materials still faces great difficulties and challenges.

To this end, in a second aspect of the invention, there is provided a two-dimensional non-layered CuGaSe₂The preparation method of the porous nano material comprises the following steps:

(1) dissolving a copper source in a reaction medium consisting of organic amine, oleic acid and octadecene to obtain a solution A.

(2) And adding the octadecylene solution dissolved with the selenium source into the preheated solution A to obtain a solution B.

(3) Adding oleylamine solution dissolved with gallium source in the process of carrying out solvothermal reaction on the solution B, continuously carrying out solvothermal reaction, and separating out a solid product after the solvothermal reaction is finished to obtain the two-dimensional non-lamellar CuGaSe₂A porous nanomaterial.

Further, in the step (1), under an oxygen isolation condition (such as in a nitrogen or inert gas atmosphere) and a stirring condition, adding the copper source into a reaction medium composed of organic amine, oleic acid and octadecene, heating to 100-180 ℃, and preserving heat to remove moisture and low-boiling-point impurities in the reaction system.

Preferably, the copper source is selected from one or more of cuprous chloride, cuprous bromide, cupric acetylacetonate or cupric acetate.

Further, in the step (1), the organic amine, the oleic acid and the octadecene are sequentially in a molar ratio of 1: 3-8: 30. Optionally, the organic amine is selected from at least one of oleylamine, octadecylamine or hexadecylamine.

Further, in the step (2), the selenium source is added into octadecene, heated to 80-200 ℃, and kept warm until the selenium source is fully dissolved. Preferably, the selenium source is selected from one or more of diphenyl diselenide, dibenzyl diselenide, selenium powder and selenium dioxide.

Further, in the step (2), the temperature of the preheated solution A is 210-230 ℃, so that the solution can be fully reacted.

Further, in the step (3), the gallium source is added into oleylamine and heated to 100-160 ℃ for heat preservation, so that the gallium source is fully dissolved. Preferably, the gallium source is selected from one or more of gallium acetylacetonate, gallium tribromide and gallium trichloride.

Further, in the step (3), the temperature of the solvent-thermal reaction of the solution B is 210-230 ℃, and the reaction time is 5-30 min.

Further, in the step (3), the temperature for continuously carrying out the solvothermal reaction is 220-260 ℃, and the reaction time is 10-120 min.

Further, the copper source, the gallium source and the selenium source are added according to the molar ratio of Cu to Ga to Se of 1:1: 2-4.

Further, in the step (3), a solid product in the reaction solution is separated by adopting a centrifugal or filtering mode, and then the solid product is washed by absolute ethyl alcohol and cyclohexane in sequence, so that a target product is obtained: two-dimensional non-laminar CuGaSe₂A porous nanomaterial.

Compared with the granular CuGaSe prepared by the traditional method₂Nano material, the two-dimensional non-layered CuGaSe of the invention₂The porous nano material has excellent absorption capacity in a visible-near infrared light range, and has good degradation of organic pollutants (such as methyl orange, rhodamine B, methylene blue and the like) and heavy metal ions (such as methyl orange, rhodamine B, methylene blue and the like) in water by taking the porous nano material as a photocatalystCr⁶⁺Etc.).

To this end, in a third aspect of the invention, there is provided said two-dimensional non-layered CuGaSe₂The application of the porous nano material in the field of photocatalysis.

Preferably, the two-dimensional non-layered CuGaSe is applied₂The porous nano material is used for photocatalytic degradation of pollutants in water.

Preferably, CuGaSe for photocatalytic degradation of pollutants in water₂The porous nano material is a plurality of pieces of the two-dimensional non-layered CuGaSe₂The porous nanometer material is self-assembled to form a multilevel structure material.

Compared with the prior art, the invention provides a liquid-phase two-step thermal injection synthesis method for preparing porous two-dimensional non-layered CuGaSe₂An effective method of a nano structure is different from the traditional method for synthesizing a two-dimensional material such as physical or chemical stripping of a layered material or vapor deposition, the liquid-phase two-step thermal injection synthesis method utilizes the characteristic that a surfactant (organic amine, oleic acid) has crystal face selective adsorption, copper selenide porous nanosheets are synthesized in the step (2) to serve as a template, then partial cation exchange reaction is further carried out in the step (3), and finally porous two-dimensional non-layered CuGaSe is realized₂Controllable preparation of nano material, the CuGaSe of the invention₂The nano material has the following beneficial effects:

in the aspects of micro appearance and structure, the CuGaSe provided by the invention₂The crystal form of the porous flaky nano material is tetragonal phase.

In terms of performance, CuGaSe with the structural characteristics₂The photocatalyst has excellent light absorption capability in a visible light range, and shows good photocatalytic performance and degradation capability when being used as a photocatalyst for degrading environmental pollutants, and the reasons are that:

（1）CuGaSe₂the self-ideal forbidden band width, high absorption coefficient and carrier mobility, especially the porous flaky shape and the self-assembled multilevel structure thereof, can absorb scattered or reflected incident light for multiple timesThereby improving the light absorption capacity of the material. In addition, the self-assembly into a multilevel structure can also effectively solve the problems of easy stacking and agglomeration among the nanosheets.

（2）CuGaSe₂The flaky porous structure has the advantages of a two-dimensional material and a porous material, can provide a larger effective specific surface area, and can accelerate mass transfer and electron transmission in the catalytic reaction process.

(3) Tetragonal phase of CuGaSe₂As a non-layered crystal structure, when the morphology is a porous two-dimensional structure, rich catalytic active sites can be provided due to the existence of surface dangling bonds.

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 Scanning Electron Microscope (SEM) photograph of the target product obtained in the first embodiment of the present invention.

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

FIG. 4 shows the photocatalytic degradation of methylene blue 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 Scanning Electron Microscope (SEM) photograph of a target product obtained by the third embodiment of the present invention.

FIG. 7 is a Scanning Electron Microscope (SEM) photograph of a target product obtained by the fourth example of the present invention.

FIG. 8 is an X-ray diffraction pattern (XRD) of a target product obtained in a fifth example of the present invention.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

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

Two-dimensional non-layered CuGaSe₂The preparation of the porous nano material comprises the following steps:

(1) adding 0.1mmol of cuprous chloride, 0.6mmol of oleylamine, 2.0mmol of oleic acid and 18mmol of octadecene into a 100ml three-necked bottle, introducing nitrogen, heating the solution to 160 ℃ 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 to obtain the solution A.

(2) Adding 2mmol of diphenyl diselenide and 30mmol of octadecene into a 50ml three-necked flask, heating to 80 ℃ and reacting for 60min to fully dissolve the diphenyl diselenide to obtain a solution B.

(3) And when the solution A is heated to 220 ℃, quickly adding the solution B containing 0.2mmol of diphenyl diselenide to obtain a solution C.

(4) Adding 1mmol of gallium acetylacetonate and 30mmol of oleylamine into a 50ml three-necked bottle, heating to 130 ℃ and reacting for 60min to fully dissolve the gallium acetylacetonate to obtain a solution D.

(5) And when the solution C reacts at 220 ℃ for 15min, quickly adding the solution D containing 0.1mmol of gallium acetylacetonate, and then continuously heating to 250 ℃ for reaction for 30 min.

(6) And (5) cooling to room temperature after the reaction in the step (5) is finished, centrifugally separating a solid product in the reaction liquid, 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

Two-dimensional non-layered CuGaSe₂The preparation of the porous nano material comprises the following steps:

(1) respectively adding 0.1mmol of cuprous bromide, 0.6mmol of octadecylamine, 3.2mmol of oleic acid and 18mmol of octadecene into a 100ml three-necked bottle, introducing nitrogen, heating the solution to 110 ℃ 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 to obtain a solution A.

(2) And (3) adding 2mmol of dibenzyl diselenide and 30mmol of octadecene into a 50ml three-necked bottle, heating to 100 ℃ and reacting for 60min to fully dissolve the dibenzyl diselenide to obtain a solution B.

(3) And when the solution A is heated to 230 ℃, quickly adding the solution B containing 0.2mmol of dibenzyl diselenide to obtain a solution C.

(4) Adding 1mmol of gallium acetylacetonate and 30mmol of oleylamine into a 50ml three-necked bottle, heating to 130 ℃, and reacting for 60min to fully dissolve the gallium acetylacetonate to obtain a solution D.

(5) And when the solution C reacts at 230 ℃ for 30min, quickly adding the solution D containing 0.1mmol of gallium acetylacetonate, and then continuously heating to 250 ℃ for reaction for 90 min.

(6) And (5) cooling to room temperature after the reaction in the step (5) is finished, centrifugally separating a solid product in the reaction liquid, 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

Two-dimensional non-layered CuGaSe₂The preparation of the porous nano material comprises the following steps:

(1) adding 0.1mmol of copper acetylacetonate, 0.6mmol of oleylamine, 3.8mmol of oleic acid and 18mmol of octadecene into a 100ml three-necked bottle, introducing nitrogen, heating the solution to 130 ℃ 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 to obtain a solution A.

(2) And adding 2mmol of selenium powder and 30mmol of octadecene into a 50ml three-necked flask, heating to 200 ℃ and reacting for 60min to fully dissolve the selenium powder to obtain a solution B.

(3) And when the solution A is heated to 220 ℃, quickly adding the solution B containing 0.2mmol of selenium powder to obtain a solution C.

(4) Adding 1mmol of gallium tribromide and 30mmol of oleylamine into a 50ml three-necked bottle, heating to 150 ℃, and reacting for 60min to fully dissolve the gallium tribromide to obtain a solution D.

(5) And when the solution C reacts for 5min at 220 ℃, quickly adding the solution D containing 0.1mmol of gallium tribromide, and then continuously heating to 260 ℃ to react for 10 min.

(6) And (5) cooling to room temperature after the reaction in the step (5) is finished, centrifugally separating a solid product in the reaction liquid, 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

Two-dimensional non-layered CuGaSe₂The preparation of the porous nano material comprises the following steps:

(1) adding 0.1mmol of copper acetate, 0.6mmol of oleylamine, 4.6mmol of oleic acid and 18mmol of octadecene into a 100ml three-necked bottle, introducing nitrogen, heating the solution to 180 ℃ under the condition of magnetic stirring, preserving the temperature for reacting for 60min, and removing water and low-boiling-point impurities in the reaction system to obtain a solution A.

(2) And (3) adding 2mmol of selenium dioxide and 30mmol of octadecene into a 50ml three-necked bottle, heating to 180 ℃ and reacting for 60min to fully dissolve the selenium dioxide to obtain a solution B.

(3) And when the solution A is heated to 210 ℃, quickly adding the solution B containing 0.2mmol of selenium dioxide to obtain a solution C.

(4) Adding 1mmol of gallium trichloride and 30mmol of oleylamine into a 50ml three-necked bottle, heating to 160 ℃, and reacting for 60min to fully dissolve the gallium trichloride to obtain a solution D.

(5) And when the solution C reacts at 210 ℃ for 10min, quickly adding the solution D containing 0.1mmol of gallium trichloride, and then continuously heating to 230 ℃ for reaction for 120 min.

(6) And (5) cooling to room temperature after the reaction in the step (5) is finished, centrifugally separating a solid product in the reaction liquid, 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

Two-dimensional non-layered CuGaSe₂The preparation of the porous nano material comprises the following steps:

(1) adding 0.1mmol of cuprous chloride, 0.6mmol of hexadecylamine, 3.8mmol of oleic acid and 18mmol of octadecene into a 100ml three-necked bottle, introducing nitrogen, heating the solution to 130 ℃ 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 to obtain a solution A.

(2) And (3) adding 2mmol of diphenyl diselenide and 30mmol of octadecene into a 50ml three-necked bottle, heating to 80 ℃ and reacting for 60min to fully dissolve the diphenyl diselenide to obtain a solution B.

(3) And when the solution A is heated to 220 ℃, quickly adding the solution B containing 0.2mmol of diphenyl diselenide to obtain a solution C.

(4) Adding 1mmol of gallium trichloride and 30mmol of oleylamine into a 50ml three-necked bottle, heating to 160 ℃, and reacting for 60min to fully dissolve the gallium trichloride to obtain a solution D.

(5) And when the solution C reacts at 220 ℃ for 20min, quickly adding the solution D containing 0.1mmol of gallium trichloride, and then continuously heating to 230 ℃ for reaction for 60 min.

(6) And (5) cooling to room temperature after the reaction in the step (5) is finished, centrifugally separating a solid product in the reaction liquid, 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

Two-dimensional non-layered CuGaSe₂The preparation of the porous nano material comprises the following steps:

(1) respectively adding 0.1mmol of cuprous bromide, 0.6mmol of octadecylamine, 1.8mmol of oleic acid and 18mmol of octadecene into a 100ml three-necked bottle, introducing nitrogen, heating the 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 to obtain a solution A.

(2) And (3) adding 2mmol of diphenyl diselenide and 30mmol of octadecene into a 50ml three-necked bottle, heating to 100 ℃ and reacting for 60min to fully dissolve the diphenyl diselenide to obtain a solution B.

(3) And when the solution A is heated to 210 ℃, quickly adding the solution B containing 0.2mmol of diphenyl diselenide to obtain a solution C.

(4) Adding 1mmol of gallium tribromide and 30mmol of oleylamine into a 50ml three-necked bottle, heating to 100 ℃, and reacting for 60min to fully dissolve the gallium tribromide to obtain a solution D.

(5) And when the C solution reacts at 210 ℃ for 10min, quickly adding the D solution containing 0.1mmol of gallium tribromide, and continuing to react at 230 ℃ for 80 min.

(6) And (5) cooling to room temperature after the reaction in the step (5) is finished, centrifugally separating a solid product in the reaction liquid, 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.

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 well indexed CuGaSe₂(JCPDS Card number 31-0456), and no other impurity peak appears, indicating that the target product prepared by the embodiment is tetragonal CuGaSe₂And (4) crystals. Likewise, the results of fig. 5 and 8 also show that the target products prepared by the second and fifth examples have the similar results to fig. 1.

FIG. 2 is a view showing the object obtained by the first embodimentScanning Electron Microscope (SEM) photograph of the product, showing the CuGaSe produced₂The porous sheet-like nano material has a thickness of about 10 to 50nm, a length of about 0.2 to 1.5um, and a pore diameter of about 2 to 80 nm. Similarly, the results in fig. 6 and 7 also show that the target products prepared by the third and fourth examples have the similar results to fig. 2.

In addition, the results of fig. 2, 6 and 7 also show that the target product exhibits: from several pieces of two-dimensional non-laminar CuGaSe₂The porous nano material is characterized by a multilevel structure formed by self-assembly, and the multilevel structure refers to a structure formed by crossing and self-assembling porous sheets to form a similar nanometer flower as shown in the figure. Compared with a single porous nanosheet, the multilevel nanostructure has the following advantages: (1) the reflected or scattered light can be absorbed multiple times, thereby improving the absorption efficiency of the incident light. (2) The problems of easy stacking and agglomeration of the nano sheets can be effectively solved.

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 two-dimensional non-lamellar CuGaSe₂The porous nano material has good absorption capacity in the visible-near infrared light range, which shows that the two-dimensional non-layered CuGaSe₂The porous nano material can be used as a catalyst to be applied to the field of photocatalysis research.

FIG. 4 shows the photocatalytic degradation of methylene blue of the product obtained in the first example, as follows: before photocatalytic degradation of methylene blue is carried out, two-dimensional non-layered CuGaSe is firstly subjected to₂The porous nano material is subjected to surface modification to enhance the water solubility. Two-dimensional non-layered CuGaSe₂The porous nano material, 0.5mL of 3-mercaptopropionic acid, 2mL of toluene and 3mL of absolute ethyl alcohol are transferred into a 10mL test tube and ultrasonically dispersed for 15min, and the test tube is stood for 24 h. Then, the solid product was washed with anhydrous ethanol by centrifugation 3 times to obtain the target product. 50mg of the target product was weighed and dispersed in 50mL of 10mg/L methylene blue aqueous solution, and stirred in a dark room for 30min to reach adsorption/desorption equilibrium. The catalytic reaction device uses a 300W xenon lamp (the optical power density is about 100 mW/cm) under the condition of circulating water cooling²) Irradiating, sucking 1.0 every 10min with a pipetteThe mL of the mixed solution was centrifuged, and the supernatant was collected. The degradation rate was calculated by measuring the absorbance at a wavelength of 664nm using an ultraviolet-visible spectrophotometer. The results are shown in fig. 4, where it can be seen that: two-dimensional non-laminar CuGaSe under irradiation of xenon lamp light source₂The porous nano material has good degradation capability on methylene blue dye.

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.