A g-C3N4 / γ-AlOOH nanocomposite material and preparation method thereof

Abstract

The present invention discloses a g-C3N4 / γ-AlOOH nanocomposite material and a preparation method thereof, belonging to the technical field of nanocomposite material preparation. The nanocomposite material is composed of g-C3N4 nanosheets and γ-AlOOH nanobelts. The preparation method comprises the following steps: preparing nanobelt-shaped γ-AlOOH by a solvothermal method, preparing g-C3N4 by a calcination method, and grinding the g-C3N4 and γ-AlOOH by a ball milling method to obtain the g-C3N4 / γ-AlOOH nanocomposite material. The nanocomposite material prepared by the present invention has good stability and reusability, and the preparation process is simple, economical, and efficient, with good application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparation of nanocomposite materials, and in particular relates to a simple and novel preparation method of a g-C3N4 and gamma-AlOOH composite. Background Art

[0002] Nanoscale materials with tailored morphologies may exhibit novel physical and chemical properties, depending on their size, shape, and exposed facets. Therefore, the preparation of materials through "nanoengineering" has become one of the most promising and challenging problems in science and technology today. Among these materials is nanoscale γ-AlOOH (boehmite), which has attracted increasing research interest in recent years in terms of synthesis methods and potential applications. Various γ-AlOOH nanostructures with controllable geometries, such as 0D nanoparticles, 1D nanorods and nanowires, and 2D nanosheets, have applications in biomedicine, environmental chemistry, catalysts, adsorbents, ceramics, and optical nanodevices.

[0003] Fast charge transfer can enhance the activity of non-radical reactions. Doping, defects, heterojunctions, and other approaches are central to the design of efficient non-radical catalysts because they can effectively modulate the electronic structure, thereby enhancing electron transfer and catalytic activity. Graphitic carbon nitride (g-C3N4) is a typical two-dimensional conjugated polymer material. It possesses an excellent electronic band structure, electron-rich properties, and high physical and chemical stability. It is particularly suitable for surface modification and composites with other materials to enhance the catalytic performance of the material.

[0004] Currently, most composite materials for g-C3N4 are prepared with oxides such as Al2O3 and ZnO using methods such as sol-gel and solvothermal methods. These methods are time-consuming, complex, and have poor reproducibility. Furthermore, no composite materials have been reported for oxyhydroxides with g-C3N4. This is because oxyhydroxides convert to oxides at high temperatures, making methods requiring heating, such as sol-gel, solid-phase, and solvothermal methods, unsuitable. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a method for compounding g-C3N4 and γ-AlOOH nanomaterials, and a g-C3N4 and γ-AlOOH nanocomposite material prepared by the above method.

[0006] The above technical problems are solved by the following technical solutions:

[0007] A g-C3N4 / γ-AlOOH nanocomposite material is formed by compounding g-C3N4 nanosheets and γ-AlOOH nanobelts, wherein the γ-AlOOH nanobelts are compounded on the surface of the g-C3N4 nanosheets, and the molar ratio of the two is 1:1. The g-C3N4 nanosheets have a diameter of 100nm-600nm, and the γ-AlOOH nanobelts have a length of 50-300nm, a width of 5-55nm, and a thickness of 2-5nm.

[0008] A preparation method of a g-C3N4 / γ-AlOOH nanocomposite material comprises the following steps: using anhydrous AlCl3, anhydrous ethanol and melamine as raw materials, firstly adding anhydrous aluminum chloride into ethanol, uniformly mixing the mixture with a magnetic stirrer, and then ultrasonically dispersing the mixture; then pouring the mixed solution into a reactor, setting the temperature to 200°C and sealing the reactor for storage for 48 hours; after the reaction is completed, naturally cooling to room temperature, washing, drying and grinding the product to obtain γ-AlOOH solid powder; calcining melamine at 550°C for 2 hours, naturally cooling to room temperature, and grinding to obtain g-C3N4; finally, placing the obtained γ-AlOOH and g-C3N4 solid powders in a molar ratio of 1:1 into a stainless steel ball mill, adding stainless steel balls for mixing, and ball milling for 10-20 hours to obtain a g-C3N4 / γ-AlOOH composite material sample powder.

[0009] Preferably, the usage ratio of anhydrous AlCl3 to anhydrous ethanol is 1g:30mL.

[0010] Preferably, the calcination is carried out in oxygen using a crucible.

[0011] Preferably, the ball milling is carried out using a planetary ball mill, the mass ratio of the total mass of the g-C3N4 and γ-AlOOH solid powders to the mass of the stainless steel balls is 1:40, and the ball milling speed is 400 rpm.

[0012] Beneficial effects:

[0013] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0014] 1. The preparation of γ-AlOOH adopts the solvothermal method, which is simple to operate, has good reproducibility and low cost. The prepared γ-AlOOH nanobelts have high yield and good purity.

[0015] 2. The present invention synthesizes a nanocomposite structure of g-C3N4 and γ-AlOOH for the first time. The composite structure of g-C3N4 and γ-AlOOH is achieved through high-energy ball milling, providing a new approach for the composite method of oxyhydroxide nanomaterials and g-C3N4 nanomaterials. The present invention uses high-energy ball milling for synthesis, which is simple to operate, has good reproducibility, and is low in cost. The prepared nanocomposite material has high yield and high purity, laying a foundation for the research of composites of oxyhydroxide materials and g-C3N4 and further application exploration. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the XRD pattern of γ-AlOOH / g-C3N4.

[0017] Figure 2 This is the TEM image of γ-AlOOH / g-C3N4.

[0018] Figure 3 This is the EDS diagram of γ-AlOOH / g-C3N4.

[0019] Figure 4 This is the HRTEM image of γ-AlOOH / g-C3N4.

[0020] Figure 5 TEM images of manually ground γ-AlOOH and g-C3N4.

[0021] Figure 6 It is the TEM image of liquid phase γ-AlOOH and g-C3N4. DETAILED DESCRIPTION

[0022] Example 1

[0023] The steps for preparing the g-C3N4 / γ-AlOOH nanocomposite material in this embodiment are as follows:

[0024] Step 1) Preparation of γ-AlOOH: Using anhydrous AlCl3 and anhydrous ethanol as raw materials, prepare a clean beaker and a magnet, measure 15ml of anhydrous ethanol with a graduated cylinder and pour it into a beaker with a volume of 50ml, then weigh 0.5g of anhydrous AlCl3 and pour it into a beaker containing 15ml of anhydrous ethanol, seal it with plastic wrap, and then stir it with a magnetic stirrer at room temperature for 30 minutes, ultrasonically disperse it for 10 minutes, and the added anhydrous AlCl3 is completely dissolved in anhydrous ethanol to form a transparent solution. The mixed solution is poured into a 25ml polytetrafluoroethylene liner, the liner is placed in the reactor shell, tightened, and then the reactor is transferred to a preheated electric constant temperature drying oven set at 200°C and kept warm for 48 hours. After the insulation is completed, the reactor is cooled to room temperature, and the translucent rubber stick product in the polytetrafluoroethylene liner is taken out. The product is placed in a beaker filled with anhydrous ethanol and ultrasonically dissolved. The solution after the dissolved product is then placed in an electric constant temperature drying oven and dried at 80°C for 10 hours. The dried product is ground to obtain white γ-AlOOH powder.

[0025] Step 2) Preparation of g-C3N4: Weigh 5 g of melamine into a crucible and calcine in a muffle furnace at 550°C for 2 h with a covered temperature of 5°C / min. Cool naturally to room temperature to obtain a pale yellow solid. Grind to a powder in an agate mortar and pestle for later use.

[0026] Step 3) Preparation of g-C3N4 / γ-AlOOH: 1 g of g-C3N4 and γ-AlOOH solid powders were weighed in a molar ratio of 1:1 and placed in a stainless steel ball mill. 40 g of stainless steel balls were added and mixed. The mixture was ball milled at 400 rpm for 10 h to obtain a g-C3N4 / γ-AlOOH sample powder, which was a g-C3N4 / γ-AlOOH composite material.

[0027] The XRD patterns of g-C3N4 / γ-AlOOH composites after ball milling for 10 h are shown in Figure 2. Figure 1 As shown, it can be seen that the XRD of g-C3N4 / γ-AlOOH is a combination of g-C3N4 and γ-AlOOH; the TEM image is as follows Figure 2 As shown, it can be seen that g-C3N4 / γ-AlOOH is γ-AlOOH nanobelts composited on the surface of g-C3N4 nanosheets; EDS diagram as shown Figure 3 As shown in the figure, it can be seen that the C, N, O, and Al element ratios of g-C3N4 / γ-AlOOH are close to 3:4:2:1; the HRTEM image is shown in Figure 4 As shown, it can be seen that g-C3N4 / γ-AlOOH are successfully composited, the nanobelts are γ-AlOOH, and the nanosheets are g-C3N4. It can be seen that the γ-AlOOH nanobelts are composited on the surface of the g-C3N4 nanosheets.

[0028] Example 2

[0029] The steps for preparing the g-C3N4 / γ-AlOOH nanocomposite material in this embodiment are as follows:

[0030] Step 1) Preparation of γ-AlOOH: Using anhydrous AlCl3 and anhydrous ethanol as raw materials, prepare a clean beaker and a magnet, measure 15ml of anhydrous ethanol with a graduated cylinder and pour it into a beaker with a volume of 50ml, then weigh 0.5g of anhydrous AlCl3 and pour it into a beaker containing 15ml of anhydrous ethanol, seal it with plastic wrap, and then stir it with a magnetic stirrer at room temperature for 30 minutes, ultrasonically disperse it for 10 minutes, and the added anhydrous AlCl3 is completely dissolved in anhydrous ethanol to form a transparent solution. The mixed solution is poured into a 25ml polytetrafluoroethylene liner, the liner is placed in the reactor shell, tightened, and then the reactor is transferred to a preheated electric constant temperature drying oven set at 200°C and kept warm for 48 hours. After the insulation is completed, the reactor is cooled to room temperature, and the translucent rubber stick product in the polytetrafluoroethylene liner is taken out. The product is placed in a beaker filled with anhydrous ethanol and ultrasonically dissolved. The solution after the dissolved product is then placed in an electric constant temperature drying oven and dried at 80°C for 10 hours. The dried product is ground to obtain white γ-AlOOH powder.

[0031] Step 2) Preparation of g-C3N4: Weigh 5 g of melamine into a crucible and calcine in a muffle furnace at 550°C for 2 h with a covered temperature of 5°C / min. Cool naturally to room temperature to obtain a pale yellow solid. Grind to a powder in an agate mortar and pestle for later use.

[0032] Step 3) Preparation of g-C3N4 / γ-AlOOH: 1 g of g-C3N4 and γ-AlOOH solid powders were weighed in a molar ratio of 1:1 and placed in a stainless steel ball mill. 40 g of stainless steel balls were added and mixed. The mixture was ball milled at 400 rpm for 15 h to obtain a g-C3N4 / γ-AlOOH sample powder, which was a g-C3N4 / γ-AlOOH composite material.

[0033] The XRD pattern of g-C3N4 / γ-AlOOH composite material after ball milling for 15h is shown in Figure 1 As shown in the TEM image Figure 2 As shown, it can be seen that g-C3N4 / γ-AlOOH is successfully composited.

[0034] Example 3

[0035] The steps for preparing the g-C3N4 / γ-AlOOH nanocomposite material in this embodiment are as follows:

[0036] Step 1) Preparation of γ-AlOOH: Using anhydrous AlCl3 and anhydrous ethanol as raw materials, prepare a clean beaker and a magnet, measure 15ml of anhydrous ethanol with a graduated cylinder and pour it into a beaker with a volume of 50ml, then weigh 0.5g of anhydrous AlCl3 and pour it into a beaker containing 15ml of anhydrous ethanol, seal it with plastic wrap, and then stir it with a magnetic stirrer at room temperature for 30 minutes, ultrasonically disperse it for 10 minutes, and the added anhydrous AlCl3 is completely dissolved in anhydrous ethanol to form a transparent solution. The mixed solution is poured into a 25ml polytetrafluoroethylene liner, the liner is placed in the reactor shell, tightened, and then the reactor is transferred to a preheated electric constant temperature drying oven set at 200°C and kept warm for 48 hours. After the insulation is completed, the reactor is cooled to room temperature, and the translucent rubber stick product in the polytetrafluoroethylene liner is taken out. The product is placed in a beaker filled with anhydrous ethanol and ultrasonically dissolved. The solution after the dissolved product is then placed in an electric constant temperature drying oven and dried at 80°C for 10 hours. The dried product is ground to obtain white γ-AlOOH powder.

[0037] Step 2) Preparation of g-C3N4: Weigh 5 g of melamine into a crucible and calcine in a muffle furnace at 550°C for 2 h with a covered temperature of 5°C / min. Cool naturally to room temperature to obtain a pale yellow solid. Grind to a powder in an agate mortar and pestle for later use.

[0038] Step 3) Preparation of g-C3N4 / γ-AlOOH: 1 g of g-C3N4 and γ-AlOOH solid powders were weighed in a molar ratio of 1:1 and placed in a stainless steel ball mill jar. 40 g of stainless steel balls were added and mixed. The mixture was ball milled at 400 rpm for 20 h to obtain a g-C3N4 / γ-AlOOH sample powder, which was a g-C3N4 / γ-AlOOH composite material.

[0039] The XRD patterns of g-C3N4 / γ-AlOOH composites after ball milling for 20h are shown in Figure 2. Figure 1 As shown in the TEM image Figure 2 As shown, it can be seen that g-C3N4 / γ-AlOOH is successfully composited.

[0040] Example 4

[0041] The steps for preparing the g-C3N4 and γ-AlOOH nanocomposite material in this embodiment are as follows:

[0042] Step 1) Preparation of γ-AlOOH: Using anhydrous AlCl3 and anhydrous ethanol as raw materials, prepare a clean beaker and a magnet, measure 15ml of anhydrous ethanol with a graduated cylinder and pour it into a beaker with a volume of 50ml, then weigh 0.5g of anhydrous AlCl3 and pour it into a beaker containing 15ml of anhydrous ethanol, seal it with plastic wrap, and then stir it with a magnetic stirrer at room temperature for 30 minutes, ultrasonically disperse it for 10 minutes, and the added anhydrous AlCl3 is completely dissolved in anhydrous ethanol to form a transparent solution. The mixed solution is poured into a 25ml polytetrafluoroethylene liner, the liner is placed in the reactor shell, tightened, and then the reactor is transferred to a preheated electric constant temperature drying oven set at 200°C and kept warm for 48 hours. After the insulation is completed, the reactor is cooled to room temperature, and the translucent rubber stick product in the polytetrafluoroethylene liner is taken out. The product is placed in a beaker filled with anhydrous ethanol and ultrasonically dissolved. The solution after the dissolved product is then placed in an electric constant temperature drying oven and dried at 80°C for 10 hours. The dried product is ground to obtain white γ-AlOOH powder.

[0043] Step 2) Preparation of g-C3N4: Weigh 5 g of melamine into a crucible and calcine in a muffle furnace at 550°C for 2 h with a covered temperature of 5°C / min. Cool naturally to room temperature to obtain a pale yellow solid. Grind to a powder in an agate mortar and pestle for later use.

[0044] Step 3) Preparation of g-C3N4 / γ-AlOOH: 1 g of solid powders of g-C3N4 and γ-AlOOH were weighed in a 1:1 molar ratio in an agate mortar and manually ground for 30 minutes to obtain a sample powder. This was not a g-C3N4 / γ-AlOOH composite material, but a simple mixture of the two.

[0045] Figure 5 This is the TEM image of manually ground γ-AlOOH and g-C3N4. γ-AlOOH and g-C3N4 are evenly dispersed, indicating that the two are not compounded.

[0046] Example 5

[0047] The steps for preparing the g-C3N4 and γ-AlOOH nanocomposite material in this embodiment are as follows:

[0048] Step 1) Preparation of γ-AlOOH: Using anhydrous AlCl3 and anhydrous ethanol as raw materials, prepare a clean beaker and a magnet, measure 15ml of anhydrous ethanol with a graduated cylinder and pour it into a beaker with a volume of 50ml, then weigh 0.5g of anhydrous AlCl3 and pour it into a beaker containing 15ml of anhydrous ethanol, seal it with plastic wrap, and then stir it with a magnetic stirrer at room temperature for 30 minutes, ultrasonically disperse it for 10 minutes, and the added anhydrous AlCl3 is completely dissolved in anhydrous ethanol to form a transparent solution. The mixed solution is poured into a 25ml polytetrafluoroethylene liner, the liner is placed in the reactor shell, tightened, and then the reactor is transferred to a preheated electric constant temperature drying oven set at 200°C and kept warm for 48 hours. After the insulation is completed, the reactor is cooled to room temperature, and the translucent rubber stick product in the polytetrafluoroethylene liner is taken out. The product is placed in a beaker filled with anhydrous ethanol and ultrasonically dissolved. The solution after the dissolved product is then placed in an electric constant temperature drying oven and dried at 80°C for 10 hours. The dried product is ground to obtain white γ-AlOOH powder.

[0049] Step 2) Preparation of g-C3N4: Weigh 5 g of melamine into a crucible and calcine in a muffle furnace at 550°C for 2 h with a covered temperature of 5°C / min. Cool naturally to room temperature to obtain a pale yellow solid. Grind to a powder in an agate mortar and pestle for later use.

[0050] Step 3) 1 g of g-C3N4 and γ-AlOOH solid powders were weighed in a molar ratio of 1:1 and placed in a beaker. 50 ml of anhydrous ethanol was added, and the mixture was stirred with a magnetic stirrer for 30 minutes, then ultrasonicated for 10 minutes, and finally dried in a constant temperature drying oven at 80°C for 10 hours. After cooling to room temperature, the powder was ground to obtain a sample. This was not a g-C3N4 / γ-AlOOH composite material, but a simple mixture of the two.

[0051] Figure 6 This is the TEM image of γ-AlOOH and g-C3N4 in the liquid phase. γ-AlOOH and g-C3N4 are evenly dispersed, indicating that the two are not compounded.

Claims

1. A g-C3N4 / γ-AlOOH nanocomposite material, which is composed of g-C3N4 nanosheets and γ-AlOOH nanobelts, wherein the γ-AlOOH nanobelts are composited on the surface of the g-C3N4 nanosheets, and the molar ratio of the two is 1:

1. The diameter of the g-C3N4 nanosheets is 100nm-600nm, and the length of the γ-AlOOH nanobelts is 50-300nm, the width is 5-55nm, and the thickness is 2-5nm.

2. A method for preparing the g-C3N4 / γ-AlOOH nanocomposite material according to claim 1, comprising: using anhydrous AlCl3, anhydrous ethanol, and melamine as raw materials, first adding anhydrous aluminum chloride to ethanol, uniformly mixing them using a magnetic stirrer, and then ultrasonically dispersing them; then pouring the mixed solution into a reactor, setting the temperature to 200°C, and sealing and storing for 48 hours; after the reaction is completed, naturally cooling to room temperature, washing, drying, and grinding the product to obtain a γ-AlOOH solid powder; calcining melamine at 550°C for 2 hours, naturally cooling to room temperature, and grinding to obtain g-C3N4; finally, placing the obtained γ-AlOOH and g-C3N4 solid powders in a molar ratio of 1:1 in a stainless steel ball mill, adding stainless steel balls to mix, and ball milling for 10-20 hours to obtain a g-C3N4 / γ-AlOOH composite material sample powder.

3. The method for preparing a g-C3N4 / γ-AlOOH nanocomposite material according to claim 2, characterized in that: The usage ratio of anhydrous AlCl3 to anhydrous ethanol is 1g:30mL.

4. The method for preparing a g-C3N4 / γ-AlOOH nanocomposite material according to claim 2, characterized in that: The calcination is carried out in oxygen using a crucible.

5. The method for preparing a g-C3N4 / γ-AlOOH nanocomposite material according to claim 2, characterized in that: The ball milling is carried out using a planetary ball mill, the mass ratio of the total mass of the g-C3N4 and γ-AlOOH solid powders to the mass of the stainless steel balls is 1:40, and the ball milling speed is 400 rpm.

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