Preparation method of g-C3N4ZnO composite material capable of efficiently degrading tetracycline

Abstract

The invention discloses a preparation method of a g-C3N4 / ZnO composite material capable of efficiently degrading tetracycline, and relates to the technical field of preparation of degraded tetracycline, and the preparation method comprises the following steps: preparing materials; uniformly mixing the graphene precursor, the zinc source material, the composite additive and the surface modifier; the mixture is subjected to a hydrothermal reaction, and a g-C3N4 / ZnO composite material is synthesized; and washing and drying the synthesized composite material to obtain the final g-C3N4 / ZnO composite material. The treated g-C3N4 / ZnO composite material is subjected to surface morphology and phase analysis, and it is ensured that the morphology and composition of the material meet the requirements. The specific surface area of g-C3N4 is increased by introducing the graphene precursor, the compounding effect of g-C3N4 and ZnO is enhanced, ZnO particles are synthesized by adopting a hydrothermal method, the photocatalytic activity is improved, efficient tetracycline degradation is achieved, the water treatment requirement is met, the manufacturing cost is reduced, and the method has industrial production potential and wide application prospects.

Description

Technical Field

[0001] This invention relates to the field of tetracycline degradation technology, specifically to a method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material. Background Technology

[0002] Tetracycline, as an antibiotic, is widely used in human, animal husbandry, and aquaculture fields. However, its excessive use has led to its accumulation in the environment, disrupting ecological balance and posing a threat to human health. Therefore, there is an urgent need to develop green, efficient, and stable methods for preparing tetracycline-degrading materials. The g-C3N4 / / ZnO heterojunction composite material based on photocatalysis technology has advantages such as being green, energy-efficient, and pollution-free, and is widely used in the degradation of tetracycline, water pollutants, CO2 reduction, and hydrogen production through water electrolysis. The preparation method plays a crucial role in the quality and photocatalytic activity of the g-C3N4 / / ZnO heterojunction. The preparation process mainly involves process parameters, ZnO doping ratio, annealing temperature, ethyl cellulose doping, preparation conditions, preparation methods, precursors, g-C3N4 doping ratio, and different heterostructure shapes. Current literature shows that researchers have improved photocatalytic activity to some extent, but the g-C3N4 / ZnO photocatalytic performance for tetracycline degradation is limited, and the performance is not very stable, with complex processes and high costs.

[0003] Therefore, the efficiency of photocatalytic degradation of tetracycline by g-C3N4 / ZnO is currently low and unstable, mainly due to the influence of the preparation of the composite material. Existing preparation processes mainly affect its cost and photocatalytic activity, limiting its further application. This invention proposes a method for preparing g-C3N4 / ZnO composite material for efficient tetracycline degradation, thereby improving the photocatalytic degradation activity of tetracycline by g-C3N4 / ZnO heterojunction. Summary of the Invention

[0004] To solve the above-mentioned technical problems, a method for preparing g-C3N4 / ZnO composite material for efficiently degrading tetracycline is provided. This technical solution solves the above-mentioned problems.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material, comprising:

[0007] The mixture contains 20-40 parts of graphene precursor, 10-30 parts of zinc source material, 5-15 parts of composite additives, 5-10 parts of surface modifiers, and 5-10 parts of moisture regulators.

[0008] Preferably, the graphene precursor includes urea and melamine nitrogen source materials, which can increase the specific surface area of ​​g-C3N4 and enhance the photocatalytic performance of the composite material; the zinc source material is one of zinc nitrate and zinc chloride, and ZnO particles are synthesized by hydrothermal method to enhance the catalytic effect of the composite material.

[0009] Preferably, the composite additive is one of sodium salt, calcium salt and aluminum salt, which enhances the interaction between g-C3N4 and ZnO, promotes electron transfer, and enhances the photocatalytic activity of the material; the surface modifier is an amino acid, surfactant or organic amine compound, which enhances the dispersibility and hydrophilicity of g-C3N4 and ZnO and improves the catalytic effect.

[0010] Preferably, the preparation steps include:

[0011] S1. Select graphene precursor, zinc source material, composite additive, surface modifier and moisture regulator according to the set ratio;

[0012] S2. Mix the graphene precursor, zinc source material, composite additives, and surface modifiers evenly to ensure uniform distribution of each component;

[0013] S3. The mixture is subjected to a hydrothermal reaction to synthesize the g-C3N4 / ZnO composite material;

[0014] S4. The synthesized composite material is washed and dried to obtain the final g-C3N4 / ZnO composite material.

[0015] S5. Perform surface morphology and phase analysis on the treated g-C3N4 / ZnO composite material to ensure that the morphology and composition of the material meet the requirements.

[0016] Preferably, S2 specifically includes:

[0017] Prepare graphene precursor, zinc source material, composite additives, surface modifiers and moisture regulators according to the set ratio;

[0018] The graphene precursor and zinc source material are pre-screened using a 60-mesh sieve to remove particles and impurities, ensuring that the raw material particles entering the mixing process are of uniform size.

[0019] Using a planetary mixer causes particles to collide and shear at high speeds within the equipment, enhancing the interaction forces between particles.

[0020] The graphene precursor, zinc source material, composite additives and surface modifiers are added to the mixing equipment one by one according to the preset ratio to make the components uniformly mixed.

[0021] Preferably, S3 specifically includes:

[0022] The mixture was added to a hydrothermal reactor and reacted under appropriate temperature and pressure conditions, with the temperature controlled between 150°C and 200°C and the reaction time between 6 and 12 hours, to ensure the synthesis of the g-C3N4-ZnO complex.

[0023] During the reaction, the pressure and temperature of the reactor are controlled to ensure that the reaction proceeds stably.

[0024] Preferably, S4 specifically includes:

[0025] The synthesized composite material was washed with deionized water to remove unreacted impurities. The washed composite material was then placed in an oven and dried at a temperature of 60°C to 80°C until the moisture content of the composite material was less than 5%.

[0026] Add 0.1–0.5 g of nitrogen carbide to the composite material and mix for half an hour. Then dry the mixture for 8 hours at a temperature of 50°C–150°C. Wash with water and ethanol and dry. Finally, calcine to obtain g-C3N4 / ZnO heterojunction material at a calcination temperature range of 300°C–600°C.

[0027] Preferably, S5 specifically includes:

[0028] X-ray diffraction (XRD) analysis was performed on the synthesized composite material to confirm its crystal phase characteristics.

[0029] The surface morphology and particle size of the composite material were observed by scanning electron microscopy (SEM).

[0030] The light absorption properties of the material were analyzed by UV-Vis absorption spectroscopy.

[0031] The component ratio of the composite material was adjusted based on the test results to optimize the photocatalytic performance.

[0032] Preferably, the diffraction peak positions of the composite material are recorded by XRD testing to analyze its crystal structure, the surface morphology and particle distribution of the composite material are recorded by SEM testing, and the light absorption range of the composite material is determined by UV-Vis testing to confirm its suitability for ultraviolet and visible light photocatalytic reactions.

[0033] Preferably, the application method of the g-C3N4 / ZnO composite material includes:

[0034] A1. Add the g-C3N4 / ZnO composite material to water in a certain proportion to form a photocatalytic reaction system;

[0035] A2. Adjust the amount of composite material and reaction conditions according to the degradation requirements of tetracycline to achieve the best degradation efficiency.

[0036] A3. Photocatalytic degradation is carried out under ultraviolet or visible light irradiation to ensure the efficient degradation reaction and reduce the concentration of tetracycline.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] This invention proposes introducing a graphene precursor to increase the specific surface area of ​​g-C3N4 and enhance its composite effect with ZnO, thereby improving photocatalytic performance and tetracycline degradation efficiency. Zinc nitrate or zinc chloride is used as the zinc source material, and ZnO particles are synthesized via a hydrothermal method to enhance the interaction between g-C3N4 and ZnO, promote electron transfer, and improve catalytic activity. A composite additive further improves the interaction between g-C3N4 and ZnO, and a surface modifier enhances dispersibility and hydrophilicity, further improving catalytic performance. This composite material can stably maintain high catalytic efficiency under ultraviolet or visible light irradiation, achieving efficient tetracycline degradation that meets water treatment requirements. Furthermore, the simple hydrothermal synthesis method is suitable for industrial production, reducing costs and showing broad application prospects. Attached Figure Description

[0039] Figure 1 This is a flowchart outlining the preparation steps of the present invention.

[0040] Figure 2 SEM images of ZnO, g-C3N4, and g-C3N4 / ZnO;

[0041] Figure 3 Activity diagrams for the degradation of tetracycline by ZnO, g-C3N4, and g-C3N4 / ZnO. Detailed Implementation

[0042] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0043] A method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material includes: 20-40 parts of graphene precursor, 10-30 parts of zinc source material, 5-15 parts of composite additive, 5-10 parts of surface modifier and 5-10 parts of moisture regulator.

[0044] The graphene precursors include urea and melamine nitrogen source materials, which can increase the specific surface area of ​​g-C3N4 and enhance the photocatalytic performance of the composite material; the zinc source material is one of zinc nitrate and zinc chloride, and ZnO particles are synthesized by hydrothermal method to enhance the catalytic effect of the composite material.

[0045] The composite additive is one of sodium, calcium, and aluminum salts, which enhances the interaction between g-C3N4 and ZnO, promotes electron transfer, and enhances the photocatalytic activity of the material; the surface modifier is an amino acid, surfactant, or organic amine compound, which enhances the dispersibility and hydrophilicity of g-C3N4 and ZnO, and improves the catalytic effect.

[0046] Reference Figure 1 As shown, the preparation steps include:

[0047] S1. Select graphene precursor, zinc source material, composite additive, surface modifier and moisture regulator according to the set ratio;

[0048] S2. Mix the graphene precursor, zinc source material, composite additives, and surface modifiers evenly to ensure uniform distribution of each component;

[0049] S3. The mixture is subjected to a hydrothermal reaction to synthesize the g-C3N4 / ZnO composite material;

[0050] S4. The synthesized composite material is washed and dried to obtain the final g-C3N4 / ZnO composite material.

[0051] S5. Perform surface morphology and phase analysis on the treated g-C3N4 / ZnO composite material to ensure that the morphology and composition of the material meet the requirements.

[0052] S2 specifically includes:

[0053] Prepare graphene precursor, zinc source material, composite additives, surface modifiers and moisture regulators according to the set ratio;

[0054] The graphene precursor and zinc source material are pre-screened using a 60-mesh sieve to remove particles and impurities, ensuring that the raw material particles entering the mixing process are of uniform size.

[0055] Using a planetary mixer causes particles to collide and shear at high speeds within the equipment, enhancing the interaction forces between particles.

[0056] The graphene precursor, zinc source material, composite additives and surface modifiers are added to the mixing equipment one by one according to the preset ratio, so that the components are mixed evenly.

[0057] S3 specifically includes:

[0058] The mixture was added to a hydrothermal reactor and reacted under appropriate temperature and pressure conditions, with the temperature controlled between 150°C and 200°C and the reaction time between 6 and 12 hours, to ensure the synthesis of the g-C3N4 / ZnO complex.

[0059] During the reaction, the pressure and temperature of the reactor are controlled to ensure that the reaction proceeds stably.

[0060] S4 specifically includes:

[0061] The synthesized composite material was washed with deionized water to remove unreacted impurities. The washed composite material was then placed in an oven and dried at a temperature of 60°C to 80°C until the moisture content of the composite material was less than 5%.

[0062] Add 0.1–0.5 g of nitrogen carbide to the composite material and mix for half an hour. Then dry the mixture for 8 hours at a temperature of 50°C–150°C. Wash with water and ethanol and dry. Finally, calcine to obtain g-C3N4 / ZnO heterojunction material at a calcination temperature range of 300°C–600°C.

[0063] S5 specifically includes:

[0064] X-ray diffraction (XRD) analysis was performed on the synthesized composite material to confirm its crystal phase characteristics.

[0065] The surface morphology and particle size of the composite material were observed by scanning electron microscopy (SEM).

[0066] The light absorption properties of the material were analyzed by UV-Vis absorption spectroscopy.

[0067] The component ratio of the composite material was adjusted based on the test results to optimize the photocatalytic performance.

[0068] XRD tests were used to record the diffraction peak positions of the composite material and analyze its crystal structure. SEM tests were used to record the surface morphology and particle distribution of the composite material. UV-Vis tests were used to determine the light absorption range of the composite material and confirm its suitability for ultraviolet and visible light photocatalytic reactions.

[0069] Application methods of g-C3N4 / ZnO composite materials include:

[0070] A1. Add the g-C3N4 / ZnO composite material to water in a certain proportion to form a photocatalytic reaction system;

[0071] A2. Adjust the amount of composite material and reaction conditions according to the degradation requirements of tetracycline to achieve the best degradation efficiency.

[0072] A3. Photocatalytic degradation is carried out under ultraviolet or visible light irradiation to ensure the efficient degradation reaction and reduce the concentration of tetracycline.

[0073] Example 1:

[0074] S1: Prepare the following components: 25 parts of graphene precursor urea, 15 parts of zinc source material zinc nitrate, 8 parts of composite auxiliary agent sodium salt, 6 parts of surface modifier amino acid, and 6 parts of moisture regulator hydrated calcium silicate.

[0075] S2: Mix the graphene precursor, zinc source material, composite additives, and surface modifiers evenly in proportion;

[0076] S3: Add the mixture to a hydrothermal reactor and react at 200°C for 8 hours;

[0077] S4: Wash and dry the product to obtain the final g-C3N4 / ZnO composite material;

[0078] S5: Ensure that the morphology and phase composition of the composite material meet the requirements through SEM and XRD analysis.

[0079] Example 2:

[0080] S1: Prepare the following components: 30 parts of graphene precursor melamine, 20 parts of zinc source material zinc chloride, 10 parts of composite auxiliary calcium salt, 7 parts of surface modifier surfactant, and 7 parts of moisture regulator gypsum.

[0081] S2: Mix the graphene precursor, zinc source material, composite additives, and surface modifiers evenly;

[0082] S3: Add the mixture to a hydrothermal reactor and react at 210°C for 9 hours;

[0083] S4: Wash and dry the synthesized items;

[0084] S5: Use SEM and XRD analysis to ensure that the dispersion and phase composition of the final composite material meet the standards.

[0085] Example 3:

[0086] S1: Prepare the following components: 28 parts of graphene precursor urea, 12 parts of zinc source material zinc nitrate, 6 parts of composite additive aluminum salt, 8 parts of surface modifier organic amine compound, and 5 parts of moisture regulator hydrated calcium silicate.

[0087] S2: Mix all components evenly according to the proportions;

[0088] S3: Add the mixture to a hydrothermal reactor and react at 190°C for 7 hours;

[0089] S4: After washing and drying, the final composite material is obtained;

[0090] S5: Perform SEM and XRD analyses to ensure the composite material meets the requirements.

[0091] Comparative Example 1:

[0092] The g-C3N4 / ZnO composite material prepared by conventional methods but not using the method of this invention has the following disadvantages:

[0093] It exhibits low photocatalytic activity and is ineffective in degrading tetracycline.

[0094] The surface morphology is uneven, and the bonding force between ZnO and g-C3N4 is poor.

[0095] Unstable; performance degrades significantly after prolonged use.

[0096] The composite material has a low specific surface area, which affects the catalytic effect.

[0097] The table below shows the properties of the g-C3N4 / ZnO composite materials prepared in different embodiments:

[0098]

[0099] The process of using this invention is as follows:

[0100] (1) Mix the zinc acetate solution evenly;

[0101] (2) Add NaOH solution dropwise to the zinc acetate solution to adjust the pH of the solution to 9-11;

[0102] (3) Add 0.1–0.5 g of nitrogen carbide and mix for half an hour;

[0103] (4) Dry the mixed solution at 50℃-150℃ for 8 hours;

[0104] (5) Wash the dried material with water and ethanol;

[0105] (6) The composite material precursor obtained after washing is baked and dried at 50℃-150℃.

[0106] (7) Calcination at 300℃-600℃ yields g-C3N4 / ZnO heterojunction material.

[0107] In summary, the advantages of this invention are as follows:

[0108] By introducing graphene precursors, the specific surface area of ​​g-C3N4 can be increased, enhancing its composite effect with ZnO, thereby improving the photocatalytic performance of the composite material and thus increasing the degradation efficiency of tetracycline.

[0109] Using zinc nitrate or zinc chloride as the zinc source material, ZnO particles can be synthesized via a hydrothermal method. This can enhance the interaction between g-C3N4 and ZnO, improve the catalytic effect of the composite material, promote efficient electron transfer, and enhance photocatalytic activity.

[0110] The addition of composite additives helps to enhance the interaction between g-C3N4 and ZnO and improve the electron migration path. At the same time, surface modifiers enhance the dispersibility and hydrophilicity of g-C3N4 and ZnO, further improving the catalytic performance of the material.

[0111] Under ultraviolet or visible light irradiation, the catalytic performance of the composite material can be maintained for a long time, and it can achieve a high tetracycline degradation efficiency in a short time, which meets the requirements of actual water treatment.

[0112] The preparation method of this invention is simple and easy to industrialize. The hydrothermal synthesis of g-C3N4 / ZnO composite material can effectively reduce production costs and has strong application prospects.

[0113] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a g-C3N4 / ZnO composite material for efficiently degrading tetracycline, characterized in that, include: The mixture contains 20-40 parts of graphene precursor, 10-30 parts of zinc source material, 5-15 parts of composite additives, 5-10 parts of surface modifiers, and 5-10 parts of moisture regulators.

2. The method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material according to claim 1, characterized in that, The graphene precursor includes urea and melamine nitrogen source materials, which can increase the specific surface area of ​​g-C3N4 and enhance the photocatalytic performance of the composite material; the zinc source material is one of zinc nitrate and zinc chloride, and ZnO particles are synthesized by hydrothermal method to enhance the catalytic effect of the composite material.

3. The method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material according to claim 1, characterized in that, The composite additive is one of sodium salt, calcium salt and aluminum salt, which enhances the interaction between g-C3N4 and ZnO, promotes electron transfer, and enhances the photocatalytic activity of the material; the surface modifier is an amino acid, surfactant or organic amine compound, which enhances the dispersibility and hydrophilicity of g-C3N4 and ZnO and improves the catalytic effect.

4. The method for preparing a highly efficient tetracycline-degrading g-C3N4ZnO composite material according to claim 1, characterized in that, The preparation steps include: S1. Select graphene precursor, zinc source material, composite additive, surface modifier and moisture regulator according to the set ratio; S2. Mix the graphene precursor, zinc source material, composite additives, and surface modifiers evenly to ensure uniform distribution of each component; S3. The mixture is subjected to a hydrothermal reaction to synthesize the g-C3N4 / ZnO composite material; S4. The synthesized composite material is washed and dried to obtain the final g-C3N4 / ZnO composite material. S5. Perform surface morphology and phase analysis on the treated g-C3N4 / ZnO composite material to ensure that the morphology and composition of the material meet the requirements.

5. The method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material according to claim 4, characterized in that, S2 specifically includes: Prepare graphene precursor, zinc source material, composite additives, surface modifiers and moisture regulators according to the set ratio; The graphene precursor and zinc source material are pre-screened using a 60-mesh sieve to remove particles and impurities, ensuring that the raw material particles entering the mixing process are of uniform size. Using a planetary mixer causes particles to collide and shear at high speeds within the equipment, enhancing the interaction forces between particles. The graphene precursor, zinc source material, composite additives and surface modifiers are added to the mixing equipment one by one according to the preset ratio to make the components uniformly mixed.

6. The method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material according to claim 4, characterized in that, S3 specifically includes: The mixture was added to a hydrothermal reactor and reacted under appropriate temperature and pressure conditions, with the temperature controlled between 150°C and 200°C and the reaction time between 6 and 12 hours, to ensure the synthesis of the g-C3N4-ZnO complex. During the reaction, the pressure and temperature of the reactor are controlled to ensure that the reaction proceeds stably.

7. The method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material according to claim 4 is characterized in that, S4 specifically includes: The synthesized composite material was washed with deionized water to remove unreacted impurities. The washed composite material was then placed in an oven and dried at a temperature of 60°C to 80°C until the moisture content of the composite material was less than 5%. Add 0.1–0.5 g of nitrogen carbide to the composite material and mix for half an hour. Then dry the mixture for 8 hours at a temperature of 50°C–150°C. Wash with water and ethanol and dry. Finally, calcine to obtain g-C3N4 / ZnO heterojunction material at a calcination temperature range of 300°C–600°C.

8. The method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material according to claim 4, characterized in that, S5 specifically includes: X-ray diffraction (XRD) analysis was performed on the synthesized composite material to confirm its crystal phase characteristics. The surface morphology and particle size of the composite material were observed by scanning electron microscopy (SEM). The light absorption properties of the material were analyzed by UV-Vis absorption spectroscopy. The component ratio of the composite material was adjusted based on the test results to optimize the photocatalytic performance.

9. The method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material according to claim 8, characterized in that: XRD tests were used to record the diffraction peak positions of the composite material and analyze its crystal structure. SEM tests were used to record the surface morphology and particle distribution of the composite material. UV-Vis tests were used to determine the light absorption range of the composite material and confirm its suitability for ultraviolet and visible light photocatalytic reactions.

10. The method for preparing a highly efficient tetracycline-degrading g-C3N4 / ZnO composite material according to claim 4, characterized in that, The application methods of the g-C3N4 / ZnO composite material include: A1. Add the g-C3N4 / ZnO composite material to water in a certain proportion to form a photocatalytic reaction system; A2. Adjust the amount of composite material and reaction conditions according to the degradation requirements of tetracycline to achieve the best degradation efficiency. A3. Photocatalytic degradation is carried out under ultraviolet or visible light irradiation to ensure the efficient degradation reaction and reduce the concentration of tetracycline.

Images