A ruthenium-doped hollow tubular molybdenum disulfide catalytic material and its preparation method

Abstract

This invention discloses a ruthenium-doped hollow tubular molybdenum disulfide catalytic material. The hollow tubular molybdenum disulfide is used as a support, and is composed of a large number of molybdenum disulfide nanosheets stacked together, with metallic Ru fixed on the support. This invention also discloses a method for preparing the above-mentioned catalytic material. This invention can prepare hollow tubular molybdenum disulfide composed of multiple tightly packed molybdenum disulfide nanosheets. The hollow tubular molybdenum disulfide support greatly promotes the dispersion of the active Ru sites on the molybdenum disulfide support and effectively reduces the aggregation and leaching of metallic Ru on the support. This results in the catalytic material having more reactive sites, thereby increasing the activation rate of PMS and achieving highly efficient catalytic degradation of carbamazepine.

Description

Technical Field

[0001] This invention relates to a ruthenium-doped hollow tubular molybdenum disulfide catalytic material, and also to a method for preparing the above-mentioned catalytic material. Background Technology

[0002] In recent years, the discharge of recalcitrant pollutants such as phenols, dyes, and pharmaceuticals into water and soil has posed a significant threat to water environment management. Methods for treating these stubborn organic pollutants, including adsorption, flocculation, membrane filtration, and microbial treatment, suffer from low efficiency, high energy consumption, and serious secondary pollution. Therefore, there is an urgent need to develop efficient, green, and low-cost technologies for wastewater treatment. In recent years, advanced oxidation processes (AOPs) based on persulfate have been considered a highly efficient method for removing recalcitrant organic matter from wastewater. This process generates a series of reactive oxidizing species (ROSs) with high activity and strong oxidizing capacity, enabling them to directly react with pollutants in water, degrading and mineralizing them into harmless small molecule compounds, thereby achieving the goal of pollutant degradation.

[0003] MoS2, a popular transition metal sulfide material, is widely used in heavy metal adsorption, photochemical processes, energy storage, and environmental remediation. MoS2 crystals consist of S-Mo-S layers, with Mo-S layers linked by covalent bonds, while the S layers are coupled through van der Waals interactions and can flexibly slide between each layer. MoS2 can act as a PMS activator; its strong affinity for PMS enables high electron mobility, generating reactive oxidizing species (ROSs) to degrade organic pollutants in aqueous solutions. However, the narrow interlayer spacing and limited active sites of a single MoS2 layer result in low catalytic activity in activating PMS for environmental remediation. Summary of the Invention

[0004] Objective of this invention: The present invention aims to provide a ruthenium-doped hollow tubular molybdenum disulfide catalytic material, which exhibits good catalytic activity, thereby effectively improving the degradation efficiency of organic pollutants (carbamazepine) in water. Another objective of this invention is to provide a method for preparing the above-mentioned catalytic material. The catalytic material prepared by this method can effectively reduce the aggregation and leaching of metal Ru ions on the support, enhance the dispersion of metal Ru on the MoS2 support, thereby giving the catalytic material more reactive sites and improving the degradation effect of activated PMS on organic pollutants in water.

[0005] Technical solution: The ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention uses hollow tubular molybdenum disulfide as a carrier. The hollow tubular molybdenum disulfide is composed of a large number of molybdenum disulfide nanosheets stacked together, and the metal Ru is fixed on the carrier by forming coordination bonds with S atoms.

[0006] The Ru loading in the catalyst is 4.5–6.8% of the catalyst mass.

[0007] The preparation method of the above-mentioned ruthenium-doped hollow tubular molybdenum disulfide catalytic material includes the following steps:

[0008] (1) Ammonium molybdate tetrahydrate, thioacetamide and tetramethylammonium bromide (which are self-sacrificing templates and gradually disappear during the reaction) are dissolved in deionized water in sequence and stirred thoroughly to obtain a suspension. The suspension is subjected to hydrothermal treatment, and after the reaction, it is filtered, washed and dried. The dried product is then heat-treated under an argon atmosphere to obtain molybdenum disulfide support.

[0009] (2) Molybdenum disulfide was mixed with an aqueous solution of ethanol and sonicated to obtain a precursor solution;

[0010] (3) Disperse trivalent ruthenium salt in deionized water by ultrasonication to obtain a ruthenium salt solution;

[0011] (4) The ruthenium salt solution was slowly added to the precursor solution. After the reaction, the Ru-MoS2 catalyst was filtered, washed and dried.

[0012] In step (1), the mass ratio of ammonium molybdate tetrahydrate, thioacetamide and tetramethylammonium bromide is 4:7:7.

[0013] In step (1), the hydrothermal treatment temperature is 180-200℃ and the time is 6-8h.

[0014] In step (1), the drying is vacuum drying, the temperature of which is 40-60℃ and the drying time is 12-48h.

[0015] In step (1), the heat treatment temperature is 300℃~600℃, and the heat treatment heating rate is 2~4℃·min. -1 The heat treatment time is 2 to 4 hours.

[0016] In step (2), the volume ratio of ethanol to water in the aqueous solution of ethanol is 7:3.

[0017] In step (3), the trivalent ruthenium salt is one of anhydrous ruthenium trichloride (RuCl3), ruthenium trichloride trihydrate (RuCl3·3H2O), or hydrated ruthenium trichloride (RuCl3·xH2O).

[0018] In step (4), the filtered solid is washed with 10 mL of water three times (each time with 10 mL of water), and then dried.

[0019] In step (4), the drying is vacuum drying, the temperature of which is 40-60℃ and the drying time is 12-48h.

[0020] The application of the ruthenium-doped hollow tubular molybdenum disulfide catalyst of this invention to degrade carbamazepine in water in the presence of PMS is as follows: The reaction solution is prepared at 15–35°C with an initial pH of 3–9. The catalyst dosage is 0.0125 g–0.075 g, the PMS dosage is 0.125 g–0.725 g, and the initial carbamazepine concentration is 20 mg·L⁻¹. -1 The catalyst activates PMS to generate singlet oxygen and superoxide radicals, which degrade carbamazepine in water, ultimately converting it into harmless small molecules (water and carbon dioxide). This invention utilizes ruthenium doping to form a composite heterogeneous catalyst, generating more adsorption and reaction centers, thereby accelerating the efficiency of carbamazepine elimination from the aquatic environment.

[0021] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: The present invention can prepare hollow tubular molybdenum disulfide composed of multiple tightly packed molybdenum disulfide nanosheets. The hollow tubular molybdenum disulfide support can greatly promote the dispersion of the metal active site Ru on the molybdenum disulfide support, and can also effectively reduce the aggregation and leaching of metal Ru on the support, thereby giving the catalytic material more reactive sites, thus improving the activation rate of PMS by the catalytic material and realizing the efficient catalytic degradation of carbamazepine by the catalyst. Attached Figure Description

[0022] Figure 1 SEM image of the catalyst material prepared in Comparative Example 1;

[0023] Figure 2 Here is a SEM image of the catalyst material prepared in Example 4;

[0024] Figure 3 The XRD patterns are of the catalysts prepared in Example 4 and Comparative Example 1.

[0025] Figure 4 The image shows a SEM image of the catalyst material prepared in Comparative Example 2.

[0026] Figure 5 The image shows the XPS plot of the catalyst material prepared in Example 4. Detailed Implementation

[0027] Example 1

[0028] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0029] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0030] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0031] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0140 g of anhydrous RuCl3 in 10 mL of water;

[0032] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0033] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of a carbamazepine (CBZ) solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalytic material was 96.7% within 120 min.

[0034] Example 2

[0035] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0036] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0037] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0038] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0154 g of anhydrous RuCl3 in 10 mL of water;

[0039] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0040] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a degradation rate of 98.5% for carbamazepine within 60 minutes.

[0041] Example 3

[0042] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0043] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0044] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0045] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0168 g of anhydrous RuCl3 in 10 mL of water;

[0046] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0047] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a degradation rate of 98.5% for carbamazepine within 45 minutes.

[0048] Example 4

[0049] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0050] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0051] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0052] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0053] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash with 10 mL of water each time, and wash three times in a row (when the amount of deionized water used each time is 10 mL, it can effectively prevent the formation of metal clusters on the support and also prevent excessive loss of ruthenium metal), and finally vacuum dry at 50°C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst material.

[0054] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a 100% degradation rate of carbamazepine within 30 minutes.

[0055] Example 5

[0056] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0057] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0058] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0059] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0190 g of anhydrous RuCl3 in 10 mL of water;

[0060] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0061] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a 97% degradation rate of carbamazepine within 60 minutes.

[0062] Example 6

[0063] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0064] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0065] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0066] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0196 g of anhydrous RuCl3 in 10 mL of water;

[0067] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0068] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a degradation rate of 98.8% for carbamazepine within 90 minutes.

[0069] Example 7

[0070] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0071] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 18 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0072] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0073] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0074] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 18 h to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0075] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalytic material was 98.4% within 30 minutes.

[0076] Example 8

[0077] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0078] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 30 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0079] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0080] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0081] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 30 h to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0082] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a degradation rate of 99.3% for carbamazepine within 30 minutes.

[0083] Example 9

[0084] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0085] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 40 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0086] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0087] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0088] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally dry it in a vacuum drying oven at 40°C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0089] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a 100% degradation rate of carbamazepine within 30 minutes.

[0090] Example 10

[0091] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0092] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 60 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0093] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0094] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0095] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally dry it in a vacuum drying oven at 60°C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0096] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a 100% degradation rate of carbamazepine within 30 minutes.

[0097] Example 11

[0098] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0099] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0100] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0101] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0173 g RuCl3·3H2O in 10 mL of water;

[0102] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0103] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a 100% degradation rate of carbamazepine within 30 minutes.

[0104] Example 12

[0105] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0106] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0107] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0108] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0179 g RuCl3·xH2O in 10 mL of water;

[0109] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0110] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a 100% degradation rate of carbamazepine within 30 minutes.

[0111] Example 13

[0112] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0113] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 300℃ and pyrolyzed for 3 hours to obtain a black powder;

[0114] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0115] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0116] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0117] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a degradation rate of 62.4% for carbamazepine within 120 min.

[0118] Example 14

[0119] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0120] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 600℃ and pyrolyzed for 3 hours to obtain a black powder;

[0121] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0122] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0123] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0124] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalytic material was 71.7% within 120 min.

[0125] Example 15

[0126] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0127] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 2 hours to obtain a black powder;

[0128] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0129] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0130] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0131] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalytic material was 92.3% within 30 minutes.

[0132] Example 16

[0133] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0134] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 4 hours to obtain a black powder;

[0135] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0136] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0137] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 10 mL of water each time, and finally vacuum dry at 50 °C for 24 hours to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0138] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalytic material was 96.4% within 30 minutes.

[0139] Example 17

[0140] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0141] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0142] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0143] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0144] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 5 mL of water each time, and finally vacuum dry at 50 °C for 24 h to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0145] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalytic material was 82.1% within 30 minutes.

[0146] Example 18

[0147] The method for preparing ruthenium-doped hollow tubular molybdenum disulfide catalytic material of the present invention includes the following steps:

[0148] (1) At room temperature, 0.494 g ammonium molybdate tetrahydrate, 0.526 g thioacetamide, and 1.078 g tetramethylammonium bromide were dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension was transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure vessel and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing was dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder was dried in a tube furnace at 2.0 °C·min under a high-purity argon atmosphere. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder;

[0149] (2) Dissolve 100 mg of black powder in an aqueous solution of ethanol (the aqueous solution of ethanol consists of 14 mL of ethanol + 6 mL of deionized water), mix under magnetic stirring and sonicate for 10 min to prepare a precursor solution.

[0150] (3) A dark brown RuCl3 solution was prepared by ultrasonically dispersing 0.0182 g of anhydrous RuCl3 in 10 mL of water;

[0151] (4) Slowly add the RuCl3 solution from step (3) to the precursor solution from step (2), stir for 2 hours, filter the obtained solid and wash it three times with 15 mL of water each time, and finally vacuum dry at 50 °C for 24 h to obtain ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0152] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalytic material was 92.8% within 30 minutes.

[0153] Example 19

[0154] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 15 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 98.7% within 120 min.

[0155] Example 20

[0156] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 35 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 100% within 20 minutes.

[0157] Example 21

[0158] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.0125 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalytic material achieved a 75% degradation rate of carbamazepine within 120 min.

[0159] Example 22

[0160] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.025 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 100% within 90 minutes.

[0161] Example 23

[0162] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.075 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 100% within 30 minutes.

[0163] Example 24

[0164] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.125 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 100% within 120 min.

[0165] Example 25

[0166] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.25 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 100% within 90 minutes.

[0167] Example 26

[0168] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.75 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 100% within 30 minutes.

[0169] Example 27

[0170] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. First, 0.2 M H₂SO₄ solution was added to the solution to adjust the initial pH to 3. Then, the suspension was stirred for 30 minutes. Finally, 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 95.6% within 30 minutes.

[0171] Example 28

[0172] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. First, 0.2 M H₂SO₄ solution was added to the solution to adjust the initial pH to 5. Then, the suspension was stirred for 30 minutes. Finally, 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 100% within 30 minutes.

[0173] Example 29

[0174] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. First, 0.2 M H₂SO₄ solution was added to the solution to adjust the initial pH to 7. Then, the suspension was stirred for 30 minutes. Finally, 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 95.2% within 30 minutes.

[0175] Example 30

[0176] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. First, 0.2 M KOH solution was added to the solution to adjust the initial pH of the reaction system to 9. Then, the suspension was stirred for 30 minutes. Finally, 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst material was 97.6% within 30 minutes.

[0177] Example 31

[0178] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. During the reaction, the pH of the reaction system was adjusted to 3 using 0.2 M H₂SO₄. The test results showed that the degradation rate of carbamazepine by the catalytic material was 96.5% within 45 minutes.

[0179] Example 32

[0180] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. During the reaction, the pH of the reaction system was adjusted to 5 using 0.2 M H₂SO₄. The test results showed that the degradation rate of carbamazepine by the catalyst material was 97.3% within 45 minutes.

[0181] Example 33

[0182] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. During the reaction, the pH of the reaction system was adjusted to 7 using 0.2 M H₂SO₄. The test results showed that the degradation rate of carbamazepine by the catalytic material was 100% within 45 minutes.

[0183] Example 34

[0184] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalytic material prepared in Example 4 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalytic material was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. During the reaction, the pH of the reaction system was adjusted to 9 using 0.2 M KOH. The test results showed that the degradation rate of carbamazepine by the catalytic material was 100% within 20 minutes.

[0185] Comparative Example 1

[0186] The preparation method of hollow tubular molybdenum disulfide catalytic material is as follows: At room temperature, 0.494 g of ammonium molybdate tetrahydrate, 0.526 g of thioacetamide, and 1.078 g of tetramethylammonium bromide are dissolved in 60 ml of deionized water. After magnetic stirring for 30 min, the resulting white suspension is transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure reactor and hydrothermally treated in an oven at 200 °C for 6 hours to obtain a dark brown mixed solution. The precipitate after filtration and washing is dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder is heated in a tube furnace under a high-purity argon atmosphere at 2.0 °C·min. -1 The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain hollow tubular molybdenum disulfide catalyst material.

[0187] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst prepared in Comparative Example 1 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C for the degradation experiment. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the degradation rate of carbamazepine by the catalyst was 51.3% within 120 min.

[0188] The hollow tubular molybdenum disulfide catalytic material prepared in Comparative Example 1 cannot effectively activate PMS in synergy with molybdenum disulfide because it does not contain ruthenium active sites. At the same time, the catalytic material has limited adsorption capacity for carbamazepine, which further leads to low degradation efficiency.

[0189] Comparative Example 2

[0190] The preparation method of ruthenium-doped hollow tubular molybdenum disulfide catalyst is as follows: At room temperature, 0.494 g of ammonium molybdate tetrahydrate, 0.526 g of thioacetamide, and 1.078 g of tetramethylammonium bromide are dissolved in 60 mL of deionized water. After magnetic stirring for 30 min, the resulting white suspension is transferred to a 100 mL polytetrafluoroethylene-lined counter-pressure reactor and hydrothermally treated in an oven at 200 °C for 6 h to obtain a dark brown mixed solution. The precipitate after filtration and washing is dried in a vacuum drying oven at 50 °C for 24 h to obtain a black powder sample. Finally, the powder is heated in a tube furnace under a high-purity argon atmosphere at 2.0 °C·min. -1The temperature was increased to 450℃ and pyrolyzed for 3 hours to obtain a black powder. 100 mg of the powder was dissolved in an aqueous solution of ethanol (14 mL ethanol + 6 mL deionized water), mixed under magnetic stirring and sonicated for 10 min to prepare a precursor solution. Then, 0.0182 g of anhydrous RuCl3 was directly dissolved in 10 mL of water to prepare a dark brown RuCl3 solution. The RuCl3 solution was slowly added to the precursor solution and stirred for another 2 hours. The obtained solid was filtered and washed with 10 mL of water each time for three consecutive washes. Finally, it was vacuum dried at 50℃ for 24 h to obtain a ruthenium-doped hollow tubular molybdenum disulfide catalyst.

[0191] The adsorption and degradation process was carried out in a 500 mL beaker, using carbamazepine as the target pollutant and PMS as the oxidant. High-performance liquid chromatography (HPLC) was used to test the performance of the catalyst prepared in Comparative Example 2 in activating PMS to degrade carbamazepine. The degradation reaction conditions were as follows: 0.05 g of the catalyst was added to 250 mL of CBZ solution with an initial concentration of 20 mg / L at 25 °C. The suspension was first stirred for 30 minutes, and then 0.5 g of PMS was added to the system to initiate the reaction. The test results showed that the catalyst exhibited a 50.8% degradation activity for carbamazepine within 30 minutes.

[0192] Compared with Example 4, the ruthenium-doped hollow tubular molybdenum disulfide catalyst prepared in Comparative Example 2 has the same Ru content. The difference is that the addition of anhydrous RuCl3 in Comparative Example 2 was not ultrasonically treated, which caused the metal Ru ions to agglomerate on the surface of the MoS2 support. The surface morphology of the catalyst material was disordered and enclosed, which greatly reduced the performance of the catalyst material.

[0193] like Figure 1 As shown, the SEM image of the MoS2 support reveals a hollow tubular morphology, consisting of a large number of molybdenum disulfide nanosheets stacked together to form a hollow tubular structure. Figure 2 As shown, the Ru-MoS2 catalyst material prepared in Example 4 still maintains a hollow tubular morphology, indicating that the molybdenum disulfide nanosheets are still relatively tightly packed after Ru doping, and the overall morphological characteristics do not change significantly. Figure 3 As shown, the catalytic material prepared in Example 4 did not show any Ru-containing signal peaks or crystalline phases in the spectrum, indicating that Ru atoms on the support are likely present in a highly dispersed manner, without aggregation. Figure 4 As shown in the figure, in the Ru-MoS2 catalytic material prepared in Comparative Example 2, the molybdenum disulfide nanosheets are stacked in a disordered and enclosed state, exhibiting agglomeration. This indicates that ultrasound can cause a large number of molybdenum disulfide nanosheets to stack in an orderly manner and enclose a hollow tubular structure, thereby promoting the high dispersion of Ru on the support. Figure 5The figure shows the XPS spectrum of the catalytic material prepared in Example 4. The characteristic peak corresponding to the Ru-S bond is shown at 280.8 eV, which proves that the metal Ru in the prepared catalytic material is fixed on the support by forming coordinate bonds with the S atoms.

Claims

1. The application of a ruthenium-doped hollow tubular molybdenum disulfide catalytic material in the degradation of carbamazepine in water, characterized in that, The specific application process is as follows: at 15~35℃, the initial pH of the reaction solution is 3~9, the amount of catalyst added is 0.0125g~0.075g, the amount of PMS is 0.125g~0.725g, and the initial concentration of carbamazepine is 20mg·L⁻¹. −1 ; The ruthenium-doped hollow tubular molybdenum disulfide catalytic material uses hollow tubular molybdenum disulfide as a support. The hollow tubular molybdenum disulfide is composed of a large number of molybdenum disulfide nanosheets stacked together, and the metal Ru is fixed on the support by forming coordination bonds with S atoms. The ruthenium-doped hollow tubular molybdenum disulfide catalytic material was prepared by the following method, with the specific steps as follows: (1) Dissolve ammonium molybdate tetrahydrate, thioacetamide and tetramethylammonium bromide in deionized water in sequence, and stir thoroughly to obtain a suspension; subject the suspension to hydrothermal treatment, filter, wash and dry after reaction, and heat-treat the dried product under argon atmosphere to obtain molybdenum disulfide; (2) Molybdenum disulfide was mixed with an aqueous solution of ethanol and sonicated to obtain a precursor solution; (3) Disperse trivalent ruthenium salt in deionized water by ultrasonication to obtain a ruthenium salt solution; (4) The ruthenium salt solution was slowly added to the precursor solution. After the reaction, the Ru-MoS2 catalyst was filtered, washed and dried.

2. The application according to claim 1, characterized in that: The Ru loading in the catalyst is 4.5 to 6.8% of the catalyst mass.

3. The application according to claim 1, characterized in that: In step (1), the mass ratio of ammonium molybdate tetrahydrate, thioacetamide and tetramethylammonium bromide is 4:7:7~8.

4. The application according to claim 1, characterized in that: In step (1), the hydrothermal treatment temperature is 180~200℃ and the time is 6~8h.

5. The application according to claim 1, characterized in that: In step (1), the heat treatment temperature is 300℃~600℃, and the heat treatment heating rate is 2~4℃·min. -1 The heat treatment time is 2 to 4 hours.

6. The application according to claim 1, characterized in that: In step (2), the volume ratio of ethanol to water in the aqueous solution of ethanol is 7:3~4.

7. The application according to claim 1, characterized in that: In step (3), the trivalent ruthenium salt is one of anhydrous ruthenium trichloride, ruthenium trichloride trihydrate, or hydrated ruthenium trichloride.

8. The application according to claim 1, characterized in that: In step (4), the filtered solid is washed with 10-15 mL of water three times in a row and then dried.

9. The application according to claim 1, characterized in that: In steps (1) and (4), the drying is vacuum drying, the temperature of vacuum drying is 40~60℃, and the drying time is 12~48h.

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