阅读说明：本技术 一种玻璃纤维布@Tb掺杂CuxTe复合材料及其制备方法 (Glass fiber cloth @ Tb doped CuxTe composite material and preparation method thereof ) 是由 江琦 吴小平 林宇昊 王朋 宋昌盛 徐凌波 崔灿 于 2021-11-04 设计创作，主要内容包括：本发明涉及一种玻璃纤维布@Tb掺杂Cu-(x)Te复合材料及制备方法,其制备方法包括以下步骤：a.将亚碲酸钠溶于丙三醇和水的混合溶液中,搅拌,形成亚碲酸钠溶液；b.将所述亚碲酸钠溶液中依次加入一定量的乙二胺四乙酸、氯化铽六水合物和无水硫酸铜,搅拌一定时间,形成混合溶液；c.将所述混合溶液和玻璃纤维布加入到四氟乙烯反应釜中,并将反应釜放到恒温箱中,恒定温度下反应一定时间后,自然冷却至室温,清洗,干燥,即得到产品玻璃纤维布@Tb掺杂Cu-(x)Te复合材料。该方法制备工艺简单,一步法获得大比表面积、均匀分散的玻璃纤维布@Tb掺杂Cu-(x)Te复合材料。(The invention relates to glass fiber cloth @ Tb doped Cu x The preparation method of the Te composite material comprises the following steps: a. dissolving sodium tellurite in a mixed solution of glycerol and water, and stirring to form a sodium tellurite solution; b. sequentially adding a certain amount of ethylene diamine tetraacetic acid, terbium chloride hexahydrate and anhydrous copper sulfate into the sodium tellurite solution, and stirring for a certain time to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, putting the reaction kettle into a constant temperature box, reacting for a certain time at a constant temperature, naturally cooling to room temperature, cleaning and drying to obtain a product of glass fiber cloth @ Tb doped with Cu x A Te composite material. The method has simple preparation process, and the uniformly dispersed glass fiber cloth @ Tb doped with Cu with large specific surface area is obtained by one-step method x A Te composite material.)

1. Glass fiber cloth @ Tb doped Cu_xThe preparation method of the Te composite material is characterized by comprising the following steps of: a. dissolving sodium tellurite in a mixed solution of glycerol and water, and stirring to form a sodium tellurite solution; b. sequentially adding a certain amount of ethylene diamine tetraacetic acid, terbium chloride hexahydrate and anhydrous copper sulfate into the sodium tellurite mixed solution, and stirring for a certain time to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for a certain time, putting the reaction kettle into a constant temperature box, reacting for a certain time at a constant temperature, naturally cooling to room temperature, cleaning, and drying to obtain a product of the glass fiber cloth @ Tb doped with Cu_xA Te composite material.

2. Glass fiber cloth @ Tb doped Cu according to claim 1_xThe preparation method of the Te composite material is characterized in that the amount of the sodium tellurite in the step a is 0.1-2.3g, the volume ratio of the glycerol to the water is 1:10-1:50, and the volume ratio of the glycerol to the water is 1: 10-10 ml.

3. Glass fiber cloth @ Tb doped Cu according to claim 1_xThe preparation method of the Te composite material is characterized in that the amount of the ethylene diamine tetraacetic acid in the step b is 0.02-0.5 g.

4. Glass fiber cloth @ Tb doped Cu according to claim 1_xThe preparation method of the Te composite material is characterized in that the amount of the terbium chloride hexahydrate in the step b is 0.0001-0.02 g.

5. Glass fiber cloth @ Tb doped Cu according to claim 1_xThe preparation method of the Te composite material is characterized in that the amount of the anhydrous copper sulfate in the step b is 0.08-3.2g, and the stirring time is 10-60 min.

6. Glass fiber cloth @ Tb doped Cu according to claim 1_xThe preparation method of the Te composite material is characterized in that the constant temperature in the step c is 150-220 ℃, and the reaction time is 2-18 h.

7. Glass fiber cloth @ Tb doped Cu according to claim 1_xThe preparation method of the Te composite material is characterized in that the ultrasonic time in the step c is 20-30 min.

8. Glass fiber cloth @ Tb doped Cu_xTe composite material, characterized in that glass fiber cloth @ Tb doped with Cu, prepared by the method according to any one of claims 1 to 7_xA Te composite material.

Technical Field

The invention relates to glass fiber cloth @ Tb doped Cu_xA preparation method of Te composite material.

Background

Tellurides have a wide range of physical and chemical properties, and besides being salt compounds, some tellurides exhibit metallic properties, while others exhibit stronger covalent properties. The literature reports that a large number of tellurium-rich tellurides all have an anionic structure with a Te — Te bond. Wherein, Cu_xTe is a black crystal powder which stably exists in air at room temperature, is an important inorganic material for storing tellurium and copper resources, and has Cu as a binary compound_xTe,Cu₂Te,Cu_xTe₂,Cu₃Te₂,Cu₇Te₄And Cu of non-stoichiometric composition_2-xTe, and the like. The copper telluride material has wide application prospect in solar cells, laser and infrared detectors and superconducting materials, and is suitable for the theme of energy conservation and environmental protection at present. The copper telluride nano material has important application prospect due to the unique micro-morphology, nano performance and special physicochemical optical characteristics displayed by the copper telluride nano material.

Although Cu_xThe preparation research of Te has made great progress, but at present, Cu_xThe preparation method of Te is complicated and the performance is not high. In order to further improve the performance, the modification can be generally carried out by doping. Rare earth is called as industrial gold, and because of excellent physical properties such as photoelectromagnetism and the like, the rare earth can form novel materials with different performances and a wide variety with other materials, and the rare earth doping also makes great progress in the development and research aspects of functional composite materials and is beneficial to improving the material performance.

In view of the above, the invention prepares the glass fiber cloth @ Tb doped with Cu by a one-step liquid phase method_xA Te composite material.

Disclosure of Invention

The inventionThe first technical problem to be solved is to provide the glass fiber cloth @ Tb doped with Cu, which has the advantages of simple process, low cost, short reaction period, uniformity, large specific surface area and high performance_xA preparation method of Te composite material.

Glass fiber cloth @ Tb doped with Cu_xThe preparation method of the Te composite material comprises the following steps: a. dissolving sodium tellurite in a mixed solution of glycerol and water, and stirring to form a sodium tellurite solution; b. sequentially adding a certain amount of ethylene diamine tetraacetic acid, terbium chloride hexahydrate and anhydrous copper sulfate into the sodium tellurite solution, and stirring for a certain time to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for a certain time, putting the reaction kettle into a constant temperature box, reacting for a certain time at a constant temperature, naturally cooling to room temperature, cleaning, and drying to obtain a product of the glass fiber cloth @ Tb doped with Cu_xA Te composite material. By the one-step method, the composite material with large specific surface and high performance can be simply and quickly prepared. And Cu is improved by doping of Tb_xBand gap of Te, increase of Cu_xThe Te structure is stable, and the catalytic performance is improved.

Further, in the step a, the amount of the sodium tellurite is 0.1-2.3g, the volume ratio of the glycerol to the water is 1:10-1:50, and the volume ratio of the glycerol to the water is 1: 10-10 ml. In which glycerol must be contained and only in the proportions indicated above, homogeneous composites with a large specific surface can be obtained. If other alcohols or proportions are used, the obtained material has uneven surface or a burr-like structure on the surface cannot be obtained.

Further, the amount of the ethylene diamine tetraacetic acid in the step b is 0.02-0.5 g.

Further, the amount of terbium chloride hexahydrate in the step b is 0.0001-0.02 g.

Furthermore, the amount of the anhydrous copper sulfate in the step b is 0.08-3.2g, and the stirring time is 10-60 min. Wherein the amount of the copper sulfate and the terbium chloride hexahydrate can be adjusted according to requirements. However, the addition of the ethylenediamine tetraacetic acid is necessary, and the terbium can be uniformly doped into the Cu only by adding the ethylenediamine tetraacetic acid in an amount of 0.02-0.5g_xIn the Te material, the material is provided with a plurality of metal layers,and the obtained surface is in a burr-shaped structure, and if the ethylene diamine tetraacetic acid or other proportions are not adopted, the surface of the material cannot be uneven or the surface cannot be in the burr-shaped structure.

Further, the ultrasonic time of the step c is 20-30 min. Ultrasonic treatment is carried out after the mixed solution is added into the reaction kettle, so that the mixed solution can be effectively contacted with the glass fiber cloth, and the coating uniformity is improved.

Further, the constant temperature of the step c is 150-220 ℃, and the reaction time is 2-18 h.

The invention also comprises glass fiber cloth @ Tb doped with Cu_xTe composite material, glass fiber cloth @ Tb doped with Cu prepared by any one of preparation methods_xA Te composite material.

Compared with the prior art, the invention has the outstanding effects that: the invention relates to glass fiber cloth @ Tb doped with Cu_xThe preparation method of the Te composite material has the advantages of simple preparation process, low requirement on equipment and high controllability. The corresponding material can be obtained only by selecting glycerol and water in a certain proportion and combining the synergistic effect of ethylene diamine tetraacetic acid in a certain proportion and specific terbium chloride and anhydrous copper sulfate, the material is uniformly coated, the surface of the material is in a burr-shaped structure, the specific surface area of the obtained material is large, and the doping of terbium can be used for improving the Cu content_xTe structural stability, increase of Cu_xPhotoelectric properties of Te. In addition, ultrasonic after the reaction kettle is added is selected, the mixed solution can be effectively contacted with the glass fiber cloth, the coating uniformity is further improved, the problem of material aggregation can be effectively solved due to the addition of the glass fiber cloth, the composite material with uniform appearance and size can be formed, and the reuse is facilitated. The glass fiber cloth @ Tb doped with Cu is realized through reasonable process control_xPreparation of Te composite material, the glass fiber cloth @ Tb is doped with Cu_xThe Te composite material has the advantages of uniform size, novel appearance and better performance, and can be widely applied to the energy and environmental protection industries.

Drawings

FIG. 1 shows the glass fiber cloth @ Tb doped with Cu prepared in example 1_xSEM photograph of Te composite.

FIG. 2 shows the glass fiber cloth @ Tb doped with Cu prepared in example 1_xSEM magnified photographs of the Te composite material.

Detailed Description

The present invention will be further illustrated by the following examples, but is not limited thereto.

Example 1

Glass fiber cloth @ Tb doped with Cu_xThe preparation method of the Te composite material comprises the following specific steps: a. dissolving 0.222g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. sequentially adding 0.2g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and 0.16g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 30min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 12h at 180 ℃, naturally cooling to room temperature, cleaning, and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

The attached figure 1-2 shows that the glass fiber cloth @ Tb prepared by the method is doped with Cu_xSEM picture of Te composite material, and from the picture, the glass fiber cloth @ Tb doped with Cu can be successfully prepared_xThe Te composite material has uniform size and uniform surface coating, the surface of the material is of a burr-shaped structure, wherein the Tb doped with Cu is coated on the surface of the glass fiber cloth_xThe Te composite material is in a structure of a burr assembly layer, has a larger specific surface, is beneficial to adsorbing other materials in the later period, and is beneficial to application such as catalysis; tb doping better modifies the material than Cu without Tb doping_xTe, the photoelectric properties of this application are all better, and can further improve specific surface with the help of glass fiber cloth, avoid gathering.

Comparative example 1, which is different from example 1 in that glycerol is not added in step a and is otherwise the same as example 1, and as a result, Tb is doped with Cu_xThe Te composite material cannot be coated on the glass fiber cloth.

Comparative example 2, which is different from example 1 in that ethylenediaminetetraacetic acid was not added in step b, and is otherwise the same as example 1,as a result, Tb was doped with Cu_xThe surface of the Te composite material is not uniformly coated and is not in a burr-shaped structure.

Comparative example 3, which is different from example 1 in that the ultrasonic step is not added in step c, but is otherwise the same as example 1, and as a result, Tb-doped Cu_xThe surface of the Te composite material is coated unevenly.

Comparative example 4, which is different from example 1 in that terbium chloride and anhydrous copper sulfate in the step c are replaced with other kinds of salts such as terbium nitrate, copper chloride, etc., and the others are the same as example 1, resulting in that Tb is doped with Cu_xThe surface of the Te composite material is not uniformly coated and is not in a burr-shaped structure. The reason is that the chlorine radical in the terbium chloride and the sulfate radical in the anhydrous copper sulfate are mutually cooperated, so that the surface appearance of the material is further improved.

Example 2

This example differs from example 1 in that the amount of sodium tellurite was changed to 0.444g, and the rest was the same as in example 1, specifically as follows: a. dissolving 0.444g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. sequentially adding 0.2g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and 0.16g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 30min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 12h at 180 ℃, naturally cooling to room temperature, cleaning, and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

Example 3

This example differs from example 1 in that the amount of anhydrous copper sulfate was changed to 0.32g, and the other examples are the same as example 1, specifically as follows: a. dissolving 0.222g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. sequentially adding 0.2g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and 0.32g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 30min to form a mixed solution; c. adding the mixed solution and glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, and addingPutting the reaction kettle into a constant temperature box, reacting for 12 hours at 180 ℃, naturally cooling to room temperature, cleaning and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

Example 4

This example differs from example 1 in that the stirring time was changed to 60min, and the rest is the same as example 1, specifically as follows: a. dissolving 0.222g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. sequentially adding 0.2g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and 0.16g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 60min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 12h at 180 ℃, naturally cooling to room temperature, cleaning, and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

Example 5

This example differs from example 1 in that the amount of ethylenediaminetetraacetic acid was changed to 0.4g, and the other steps are the same as in example 1, specifically as follows: a. dissolving 0.222g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. sequentially adding 0.4g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and 0.16g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 30min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 12h at 180 ℃, naturally cooling to room temperature, cleaning, and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

Example 6

This example differs from example 1 in that the reaction temperature was changed to 200 ℃ and otherwise the same as example 1, specifically as follows: a. dissolving 0.222g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. 0.2g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and sodium tellurite solution are sequentially added into the sodium tellurite solution0.16g of anhydrous copper sulfate, stirring for 30min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, carrying out ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 12h at 200 ℃, naturally cooling to room temperature, cleaning and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

Example 7

This example differs from example 1 in that the reaction time was changed to 18h, otherwise the same as example 1, as follows: a. dissolving 0.222g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. sequentially adding 0.2g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and 0.16g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 30min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 18h at 180 ℃, naturally cooling to room temperature, cleaning, and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

Example 8

This example differs from example 1 in that the amount of terbium chloride hexahydrate was changed to 0.01g, and the other examples are the same as example 1, specifically as follows: a. dissolving 0.222g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. sequentially adding 0.2g of ethylene diamine tetraacetic acid, 0.01g of terbium chloride hexahydrate and 0.16g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 30min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 12h at 180 ℃, naturally cooling to room temperature, cleaning, and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

Example 9

This example differs from example 1 in that the amounts of glycerin and water were changed to 6ml and 94ml, respectively, and the other examples are the same as example 1, specifically as follows: a. 0.222g of sodium tellurite was dissolved in 6ml of propyleneStirring the mixed solution of the triol and 94ml of water to form a sodium tellurite solution; b. sequentially adding 0.2g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and 0.16g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 30min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 12h at 180 ℃, naturally cooling to room temperature, cleaning, and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.

Example 10

This example differs from example 1 in that the amount of anhydrous copper sulfate was changed to 0.08g, and the other examples are the same as example 1, specifically as follows: a. dissolving 0.222g of sodium tellurite in a mixed solution of 3ml of glycerol and 47ml of water, and stirring to form a sodium tellurite solution; b. sequentially adding 0.2g of ethylene diamine tetraacetic acid, 0.005g of terbium chloride hexahydrate and 0.08g of anhydrous copper sulfate into the sodium tellurite solution, and stirring for 30min to form a mixed solution; c. adding the mixed solution and the glass fiber cloth into a tetrafluoroethylene reaction kettle, performing ultrasonic treatment for 25min, putting the reaction kettle into a thermostat, reacting for 12h at 180 ℃, naturally cooling to room temperature, cleaning, and drying to obtain the product glass fiber cloth @ Tb doped with Cu_xA Te composite material.