Preparation method of carbon skeleton supported ultra-thin titanium disulfide nanosheet photocatalytic material

Abstract

The application provides a preparation method of a carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material. Organic titanium salt and sulfur-containing functional group organic compounds are added into a mixed solution of ethylene glycol and deionized water, magnetic stirring is carried out, then hollow tube carbon skeletons are added into the solution, ultrasonic dispersion is carried out, and the solution is recorded as solution A; A is transferred into a reaction kettle, after heating, the solution is naturally cooled to room temperature, filtration, washing and drying are carried out, and B is obtained; B is dispersed into a buffer solution, ultrasonic dispersion is carried out, dopamine hydrochloride is added into the suspension, magnetic stirring is carried out, the precipitate is centrifuged, the obtained product is dried in a vacuum oven, and C is obtained; C is heated and calcined in an argon mixed gas atmosphere containing hydrogen, and the final product, the carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material, is obtained. In the dark, the adsorption of the carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material to tetracycline reaches equilibrium, then under the condition of ultraviolet photocatalysis, after 60 min, the degradation of tetracycline reaches 99.3%.

Description

TECHNICAL FIELD

[0001] The application relates to a photocatalytic material, in particular to a preparation method of a carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material. BACKGROUND

[0002] With the development of chemical industry, environmental pollution is becoming increasingly serious. Discharge of printing and dyeing wastewater is one of the important reasons for water pollution. A large amount of commercial dyes are discharged every year, which are stable in chemical properties and cause great harm to the ecological environment. The semiconductor oxide material can be activated under sunlight, and can effectively oxidize and degrade organic matters into small molecules such as carbon dioxide and water. Compared with traditional purification methods, the semiconductor photocatalytic technology has the advantages of mild reaction conditions, no secondary pollution, simple operation and obvious degradation effect. Titanium dioxide is one of the photocatalysts that are concerned, and has the advantages of low toxicity, low cost, durability, super hydrophilicity and excellent photochemical stability.

[0003] Transition metal dichalcogenides are an important class of materials, which have attracted much attention due to their rich physical and chemical properties. In particular, MoS2, WS2 and WSe2, as typical transition metal dichalcogenides, have shown rich phenomena in the fields of optoelectronics, energy valley electronics and spin electronics, which have aroused widespread research interest. Recent studies have shown that titanium disulfide in transition metal dichalcogenides has attracted widespread attention in the fields of nanoelectronics, photonics, sensors and energy storage system electrodes. It can be used in the field of photocatalysis. SUMMARY

[0004] In order to overcome the shortcomings of the prior art, the application aims to provide a preparation method of a carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material.

[0005] Another purpose of the application is the product obtained by the above method.

[0006] Still another purpose of the application is the application of the above product.

[0007] The purpose of the application is achieved by the following scheme: a preparation method of a carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material, the specific steps are as follows:

[0008] Step 1: 0.02-0.04 mmol of organic titanium salt and 0.04-0.08 mmol of sulfur-containing functional group organic compound are added to a mixed solution of 80 mL of ethylene glycol and deionized water (the volume ratio of the two is 1-2:1), and then the hollow tube carbon skeleton is added and ultrasonically dispersed for 20-30 min to make it uniformly dispersed, so that the solution is fully mixed, and the solution is recorded as solution A;

[0009] Second step: transfer the above solution A to the reaction kettle, heat to 200-240 DEG C reaction for 20-30 h, the solution is naturally cooled to room temperature, the resulting precipitate is filtered, washed with deionized water and organic solvent 3-5 times and dried in a vacuum drying oven at 100-120 DEG C, B is obtained;

[0010] Third step: the B obtained in the second step is dispersed into 100 mL buffer solution and ultrasonically dispersed, 40-60 mg of dopamine hydrochloride is added to the suspension and magnetically stirred for 20-30 h, the precipitate is centrifuged and separated, and the resulting product is dried in a vacuum oven at 60-80 DEG C, C is obtained.

[0011] Fourth step: C is heated to 500-600 DEG C at a heating and cooling rate of 1-2 DEG C / min in an argon gas mixture atmosphere containing 5% hydrogen by volume, and is kept at this temperature for 2-4 h to obtain the final product, a carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material.

[0012] The application provides a preparation method of a carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material.

[0013] The organic titanium salt is one or a combination of tetrabutyl titanate, isopropyl titanate or ethyl titanate.

[0014] The sulfur-containing functional group is one or a combination of thiourea, mercaptan or sulfur-containing amino acid.

[0015] The application provides a product obtained by the above method.

[0016] The application also provides application of the product in catalytic degradation of tetracycline.

[0017] Compared with the prior art, the application has the following beneficial effects: the application provides a preparation method of a carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material, the carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material has a large specific surface area, plays a very important role in improving the photocatalytic performance of the material, is beneficial to improving the photocatalytic performance of the material, and the preparation process is relatively simple and easy to operate. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is a photocatalytic performance diagram of the carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material in Example 1. DETAILED DESCRIPTION

[0019] The present application is described in detail by the following specific examples, but the scope of protection of the present application is not limited to these examples.

[0020] Example 1

[0021] A carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material is prepared by the following steps:

[0022] First step: 0.02 mmol of organic titanium salt tetrabutyl titanate and 0.04 mmol of sulfur-containing functional group organic compound l-thiourea are added to a mixed solution of 80 mL of ethylene glycol and deionized water, the volume ratio of which is 1:1, and magnetic stirring is performed, then hollow tube carbon skeleton is added thereto, ultrasonic dispersion is performed for 20 min to make it uniformly dispersed, and the solution is fully mixed, which is denoted as solution A;

[0023] Second step: After the above solution A is transferred to a reaction kettle and heated to 200 ℃ for 30 h, the solution is naturally cooled to room temperature, the obtained precipitate is filtered, washed with deionized water and an organic solvent for 3-5 times, and then dried in a vacuum drying oven at 100 ℃, to obtain B;

[0024] Third step: B obtained in the second step is dispersed into 100 mL of a buffer solution to obtain a suspension; 40 mg of dopamine hydrochloride is added to the suspension and magnetically stirred for 20 h, the precipitate is centrifuged and separated, and the obtained product is dried in a vacuum oven at 80 ℃, to obtain C;

[0025] Fourth step: C is heated to 500 ℃ at a heating rate of 2 ℃ / min in an argon gas mixed gas atmosphere containing 5% hydrogen by volume, and kept for 4 h, to obtain the final product, a carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material.

[0026] Figure 1 is a photocatalytic performance diagram of the carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material, in the dark, the adsorption of the carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material to tetracycline reaches equilibrium first, then under the condition of ultraviolet photocatalysis, after 60 min, the degradation of tetracycline reaches 99.3%.

[0027] Example 2

[0028] A carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material is prepared by the following steps:

[0029] First step: 0.02 mmol of organic titanium salt titanium ethyl propyl ester and 0.04 mmol of mercaptan are added to a mixed solution of 80 mL of ethylene glycol and deionized water in a volume ratio of 2:1, magnetic stirring is carried out, then hollow tube carbon skeleton is added, ultrasonic dispersion is carried out for 30 min to make it uniformly dispersed, and the solution is fully mixed, and the solution is recorded as solution A;

[0030] Second step: solution A is transferred to a reaction kettle, heated to 220 DEG C and reacted for 30 h, then the solution is naturally cooled to room temperature, the obtained precipitate is filtered, washed with deionized water and an organic solvent for 3 times, and then dried in a vacuum drying oven at 120 DEG C, and B is obtained;

[0031] Third step: B obtained in the second step is dispersed into 100 mL of a buffer solution to obtain a suspension; 40 mg of dopamine hydrochloride is added to the suspension and magnetically stirred for 20 h, the precipitate is centrifugally separated, the obtained product is dried in a vacuum oven at 80 DEG C, and C is obtained;

[0032] Fourth step: C is heated to 550 DEG C at a temperature rising rate of 2 DEG C / min in an argon mixed gas atmosphere containing 5% hydrogen by volume, and kept for 3 h, and a final product of carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material is obtained.

[0033] Example 3

[0034] A carbon skeleton supported ultrathin titanium disulfide nanosheet photocatalytic material is prepared according to the following steps:

[0035] First step: 0.02 mmol of organic titanium salt titanium ethyl propyl ester and 0.04 mmol of sulfur-containing amino acid are added to a mixed solution of 80 mL of ethylene glycol and deionized water in a volume ratio of 2:1, magnetic stirring is carried out, then hollow tube carbon skeleton is added, ultrasonic dispersion is carried out for 30 min to make it uniformly dispersed, and the solution is fully mixed, and the solution is recorded as solution A;

[0036] Second step: solution A is transferred to a reaction kettle, heated to 240 DEG C and reacted for 20 h, then the solution is naturally cooled to room temperature, the obtained precipitate is filtered, washed with deionized water and an organic solvent for 3 times, and then dried in a vacuum drying oven at 120 DEG C, and B is obtained;

[0037] Third step: B obtained in the second step is dispersed into 100 mL of a buffer solution to obtain a suspension; 60 mg of dopamine hydrochloride is added to the suspension and magnetically stirred for 25 h, the precipitate is centrifugally separated, the obtained product is dried in a vacuum oven at 80 DEG C, and C is obtained;

[0038] Fourth step: C is placed in the argon mixed gas atmosphere containing 5% hydrogen by volume, heated to 600 ℃ at a heating and cooling rate of 2 ℃ / min, and kept for 2 h to obtain the final product of carbon skeleton supported ultra-thin titanium disulfide nanosheet photocatalytic material.

Claims

1. The application of a carbon-framework-supported ultrathin titanium disulfide nanosheet photocatalytic material in the catalytic degradation of tetracycline, characterized in that, The method for preparing the carbon framework-supported ultrathin titanium disulfide nanosheet photocatalytic material includes the following steps. Step 1: Add 0.02-0.04 mmol of organic titanium salt and 0.04-0.08 mmol of sulfur-containing organic compound to a mixed solution of 80 mL of ethylene glycol and deionized water and stir magnetically. The volume ratio of ethylene glycol to deionized water is 1-2:

1. Then add a hollow carbon skeleton and ultrasonically disperse for 20-30 min to ensure uniform dispersion and thorough mixing. This solution is denoted as solution A. Step 2: Transfer the above solution A to a reaction vessel, heat to 200-240 ℃ and react for 20-30 h. After the solution cools naturally to room temperature, filter the obtained precipitate, wash it 3-5 times with deionized water and organic solvent, and then dry it in a vacuum drying oven at 100-120 ℃ to obtain B. Step 3: Disperse B obtained in Step 2 into 100 mL of buffer solution and sonicate to obtain a suspension. Add 40-60 mg of dopamine hydrochloride to the suspension and stir magnetically for 20-30 h. Centrifuge the precipitate and dry the obtained product in a vacuum oven at 60-80 ℃ to obtain C. Step 4: Place C in an argon mixed atmosphere containing 5% hydrogen by volume and heat it to 500-600 ℃ at a heating rate of 1-2 ℃ / min. Hold the temperature for 2-4 h to obtain the final product, carbon framework supported ultrathin titanium disulfide nanosheet photocatalytic material. The organic titanium salt is one or a combination of tetrabutyl titanate, isopropyl titanate, and ethyl titanate.

2. The application of the carbon framework supported ultrathin titanium disulfide nanosheet photocatalytic material according to claim 1, characterized in that... The sulfur-containing functional group is one or a combination of thiourea, thiols, or sulfur-containing amino acids.

3. The application of the carbon framework supported ultrathin titanium disulfide nanosheet photocatalytic material according to any one of claims 1 to 2, characterized in that, Prepare according to the following steps: Step 1: Add 0.02 mmol of the organic titanium salt tetrabutyl titanate and 0.04 mmol of thiourea to a mixed solution of 80 mL of ethylene glycol and deionized water, wherein the volume ratio of ethylene glycol to deionized water is 1:

1. Stir magnetically, then add the hollow tube carbon skeleton and ultrasonically disperse for 20 min to make it evenly dispersed and the solution fully mixed. This solution is denoted as solution A. Step 2: Transfer the above solution A to a reaction vessel, heat to 200 ℃ and react for 30 h. After the solution cools naturally to room temperature, filter the obtained precipitate, wash it 3-5 times with deionized water and organic solvent, and then dry it in a vacuum drying oven at 100 ℃ to obtain B. Step 3: Disperse the B obtained in Step 2 into 100 mL of buffer solution and sonicate to obtain a suspension; 40 mg of dopamine hydrochloride was added to the suspension and stirred magnetically for 20 h. The precipitate was separated by centrifugation, and the resulting product was dried in a vacuum oven at 80 °C to obtain C. Step 4: Place C in an argon mixed atmosphere containing 5% hydrogen by volume and heat it to 500℃ at a heating rate of 2℃ / min. Hold the temperature for 4 h to obtain the final product, carbon framework supported ultrathin titanium disulfide nanosheet photocatalytic material.

4. The application of a carbon framework-supported ultrathin titanium disulfide nanosheet photocatalytic material according to any one of claims 1 to 2, characterized in that, Prepare according to the following steps: Step 1: Add 0.02 mmol of organic titanium salt ethyl propylene titanate and 0.04 mmol of thiol to a mixed solution of 80 mL of ethylene glycol and deionized water and stir magnetically. The volume ratio of ethylene glycol to deionized water is 2:

1. Then add a hollow carbon skeleton and ultrasonically disperse for 30 min to make it evenly dispersed and the solution fully mixed. This solution is denoted as solution A. Step 2: Transfer the above solution A to a reaction vessel, heat it to 220 ℃ and react for 30 h. After the solution cools naturally to room temperature, filter the obtained precipitate, wash it three times with deionized water and organic solvent, and then dry it in a vacuum drying oven at 120 ℃ to obtain B. Step 3: Disperse the B obtained in Step 2 into 100 mL of buffer solution and sonicate to obtain a suspension; 40 mg of dopamine hydrochloride was added to the suspension and stirred magnetically for 20 h. The precipitate was separated by centrifugation, and the resulting product was dried in a vacuum oven at 80 °C to obtain C. Step 4: Place C in an argon mixed atmosphere containing 5% hydrogen by volume and heat it to 550 ℃ at a heating rate of 2 ℃ / min. Hold the temperature for 3 h to obtain the final product, carbon framework supported ultrathin titanium disulfide nanosheet photocatalytic material.

5. The application of a carbon framework-supported ultrathin titanium disulfide nanosheet photocatalytic material according to any one of claims 1 to 2, characterized in that, Prepare according to the following steps: Step 1: Add 0.02 mmol of organic titanium salt ethyl propylene titanate and 0.04 mmol of sulfur-containing amino acids to a mixed solution of 80 mL of ethylene glycol and deionized water and stir magnetically. The volume ratio of ethylene glycol to deionized water is 2:

1. Then, add a hollow carbon skeleton and ultrasonically disperse for 30 min to ensure uniform dispersion and thorough mixing. This solution is denoted as solution A. Step 2: Transfer the above solution A to a reaction vessel, heat it to 240℃ and react for 20 h. After the solution cools naturally to room temperature, filter the obtained precipitate, wash it three times with deionized water and organic solvent, and then dry it in a vacuum drying oven at 120℃ to obtain B. Step 3: Disperse B obtained in Step 2 into 100 mL of buffer solution by ultrasonic dispersion to obtain a suspension; add 60 mg of dopamine hydrochloride to the suspension and stir magnetically for 25 h; separate the precipitate by centrifugation; and dry the obtained product in a vacuum oven at 80 °C to obtain C. Step 4: Place C in an argon mixed atmosphere containing 5% hydrogen by volume and heat it to 600 ℃ at a heating rate of 2 ℃ / min. Hold the temperature for 2 h to obtain the final product, carbon framework supported ultrathin titanium disulfide nanosheet photocatalytic material.

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