Nano heterojunction material for photodegradation of tetracycline as well as preparation method and application of nano heterojunction material

Abstract

The invention discloses a nano heterojunction material for photodegradation of tetracycline as well as a preparation method and application of the nano heterojunction material. The nano heterojunction material is formed by compounding a metal organic framework material and an indium vacancy-containing zinc indium sulfide ternary semiconductor material, the indium vacancy-containing zinc indium sulfide ternary semiconductor material is obtained through solvothermal reaction of metal nitrate containing zinc nitrate and indium nitrate and a first organic ligand containing sulfydryl; the metal organic framework material is constructed by taking porphyrin or a porphyrin derivative as a second organic ligand. Under the irradiation of visible light, 99.8% of tetracycline can be degraded by the nano heterojunction only within 0.5 hour, and after continuous five degradation operations, the photocatalytic degradation rate is kept at 98%. The material has the advantages of wide spectral absorption range, excellent photocurrent response characteristic, efficient carrier separation and electron transfer rate and excellent environmental stability, and can maintain efficient photocatalytic degradation capacity in a complex water body environment.

Description

Technical Field

[0001] The invention relates to the technical field of environmentally friendly materials, and in particular to a nano heterojunction material for photodegrading tetracycline, and a preparation method and application thereof. Background Art

[0002] As a typical representative of broad-spectrum antibiotics, tetracycline has shown extraordinary potential and important value in the medical field. However, with its widespread use in agricultural production, animal husbandry and human medicine, the abuse of antibiotics has caused a series of environmental problems. A large number of antibiotics are directly released into the water without proper treatment, and they continue to exist and accumulate, which not only seriously damages the balance of the aquatic ecosystem, but also passes through the food chain, posing a potential threat to the health of humans and other organisms. What is more serious is that the abuse of antibiotics has also accelerated the development of bacterial resistance. This phenomenon not only seriously undermines water quality standards, but also poses a long-term and complex public health risk, posing a hidden danger to public health.

[0003] At present, traditional wastewater treatment technologies such as coagulation, biological treatment and adsorption have exposed obvious limitations in treating antibiotic pollution, such as high energy consumption, low removal efficiency and incomplete degradation. Especially for some high-concentration or difficult-to-degrade antibiotic wastewater, the effects of these methods cannot meet the needs. In view of this, actively exploring and developing new, efficient and energy-saving antibiotic degradation technologies and materials has become an important issue that needs to be solved urgently.

[0004] Photocatalytic degradation technology, with its mild reaction conditions, strong oxidation ability, economical cost, good environmental adaptability and efficient degradation characteristics, without the need to add additional chemical reagents, has become the focus of research in recent years and has received widespread attention. This technology has shown significant advantages in alleviating the toxicity of antibiotic pollutants, especially in the pretreatment of high-concentration antibiotic wastewater and the deep purification of trace antibiotics, its application potential is particularly prominent. However, the current technical system still faces several core challenges, including the relatively narrow light absorption spectrum range, which limits the full utilization of light energy; the rapid recombination of photogenerated carriers (electron-hole pairs), which hinders the improvement of catalytic efficiency; and the insufficient stability of the catalyst in long-term operation, which affects its ability to continuously and efficiently degrade antibiotics.

[0005] Metal-organic framework materials, with their customizable structure and tunable properties, have become one of the most promising materials in the field of photocatalytic degradation. In particular, metal-organic framework materials constructed with porphyrin as ligands, such as PCN224, not only exhibit good acid-base stability, but also have excellent light absorption ability and high charge separation efficiency. However, the light absorption range of a single metal-organic framework material is often limited, and it is impossible to fully utilize the full spectrum energy in sunlight. Secondly, the recombination rate of photogenerated electrons and holes within a single material is high, resulting in limited photocatalytic efficiency. In addition, a single material may lack sufficient catalytic selectivity and stability when facing complex environmental pollutants. Summary of the invention

[0006] In order to overcome the limitations of the prior art, constructing a heterojunction has become an effective strategy to improve photocatalytic performance. By combining different materials to form a heterojunction, the advantages of each component material can be fully utilized to achieve complementary and optimized photocatalytic performance. Therefore, the present invention provides a new type of nano heterojunction material photocatalyst, which achieves efficient degradation of tetracycline, an antibiotic pollutant in aquatic environment, by combining a metal organic framework material with a zinc indium sulfide ternary semiconductor material.

[0007] The present invention provides a nano heterojunction material for photodegradation of tetracycline, which is composited with a metal organic framework material and a zinc indium sulfide ternary semiconductor material containing indium vacancies;

[0008] The zinc indium sulfide ternary semiconductor material containing indium vacancies is obtained by a solvothermal reaction of a metal nitrate comprising zinc nitrate and indium nitrate or a metal chloride comprising zinc chloride and indium chloride with a first organic ligand containing a mercapto group;

[0009] The metal organic framework material is a metal organic framework material constructed with porphyrin or a porphyrin derivative as the second organic ligand.

[0010] Preferably, the metal organic framework material is PCN224 or a functionalized derivative of PCN224.

[0011] In some embodiments of the present invention, the first organic ligand containing a thiol group is cysteine;

[0012] The second organic ligand is at least one of porphyrin, iron porphyrin, copper porphyrin, palladium porphyrin, platinum porphyrin and manganese porphyrin.

[0013] Preferably, when the raw material is metal nitrate, the mass ratio of zinc nitrate, indium nitrate and cysteine ​​is 1:2-3:1-2; when the raw material is metal chloride, the mass ratio of zinc chloride, indium chloride and cysteine ​​is 1:3-4:2-3.

[0014] More preferably, when the raw material is metal nitrate, the mass ratio of zinc nitrate, indium nitrate and cysteine ​​is 1:2.37:1; when the raw material is metal chloride, the mass ratio of zinc chloride, indium chloride and cysteine ​​is 1:3.5:2.

[0015] The present invention also provides a method for preparing a nano heterojunction material for photodegradation of tetracycline, comprising the following steps:

[0016] a) dissolving a metal nitrate or a metal chloride and a first organic ligand containing a thiol group in deionized water respectively, and obtaining a zinc indium sulfide material containing an indium vacancy by a solvothermal reaction;

[0017] The metal nitrates include zinc nitrate and indium nitrate; the metal chlorides include zinc chloride and indium chloride;

[0018] b) dispersing the zinc indium sulfide material containing indium vacancies obtained in step a) in an organic solvent, mixing it with a zirconium salt and a second organic ligand to carry out a solvothermal reaction, so as to obtain a nano-heterojunction material composite of a metal organic framework and zinc indium sulfide;

[0019] The second organic ligand is porphyrin or a porphyrin derivative.

[0020] In some embodiments of the present invention, the first organic ligand containing a thiol group is cysteine;

[0021] When the raw material is metal nitrate, the mass ratio of zinc nitrate, indium nitrate and cysteine ​​is 1:2-3:1-2; when the raw material is metal chloride, the mass ratio of zinc chloride, indium chloride and cysteine ​​is 1:3-4:2-3.

[0022] Preferably, when the raw material is metal nitrate, the mass ratio of zinc nitrate, indium nitrate and cysteine ​​is 1:2.37:1; when the raw material is metal chloride, the mass ratio of zinc chloride, indium chloride and cysteine ​​is 1:3.5:2.

[0023] The specific steps of step a) are:

[0024] Dissolve zinc nitrate, indium nitrate and cysteine ​​in deionized water to obtain a mixed solution; mix the two bottles of solution in the inner tank of a hydrothermal reactor after ultrasonic treatment until the metal salt is dissolved and the organic ligand is evenly dispersed; put the reactor into a 160°C constant temperature oven. Take out the reactor after 18 hours and cool it naturally; wash the obtained powder with ethanol and water for 3 times respectively, and then dry it in an 80°C oven to obtain a zinc indium sulfide material containing indium vacancies.

[0025] In some embodiments of the present invention, in step b), the organic solvent is N,N-dimethylformamide;

[0026] The zirconium salt is zirconium oxychloride;

[0027] The second organic ligand is at least one of porphyrin, iron porphyrin, copper porphyrin, palladium porphyrin, platinum porphyrin and manganese porphyrin;

[0028] The mass ratio of the zirconium salt to the second organic ligand is 3:1.

[0029] In some embodiments of the present invention, in step a), the temperature of the solvent thermal reaction is 155-165° C. and the time is 16-18 hours; in step b), the temperature of the solvent thermal reaction is 85-95° C. and the time is 4-5 hours.

[0030] The specific steps of step b) are:

[0031] The dried zinc indium sulfide material containing indium vacancies is dispersed in N,N-dimethylformamide, zirconium oxychloride, porphyrin and benzoic acid are dissolved in N,N-dimethylformamide, the two are mixed in a three-necked flask, and placed in an oil bath at 90°C for 5 hours; the obtained powder is washed three times with ethanol and then dried in an oven at 80°C to obtain a nano-heterojunction material composite of a metal organic framework and zinc indium sulfide.

[0032] The invention also provides application of the nano heterojunction material for photodegradation of tetracycline in photocatalytic degradation of tetracycline.

[0033] The invention also provides a method for photocatalytic degradation of tetracycline, wherein the nano heterojunction material for photodegradation of tetracycline is added into a water body polluted by tetracycline, and then photocatalytic degradation is performed to degrade the tetracycline.

[0034] Under the irradiation of visible light, the material can achieve 99.8% efficient degradation of tetracycline in a very short time (only 0.5 hours). Even after five consecutive degradation operations, its photocatalytic performance remains the same, demonstrating the material's long-lasting effectiveness and stability in treating tetracycline-contaminated water.

[0035] The specific beneficial effects of the present invention are:

[0036] 1. The present invention adopts a solvothermal method to prepare a nano heterojunction, which is simple and easy to operate, with mild reaction conditions and a yield of up to 70% to 80%. In the entire preparation process, the raw materials used are non-toxic and harmless, and the generation of toxic and harmful substances is avoided. In the prepared nano heterojunction, the porphyrin-based metal organic framework material is evenly covered on the surface of the zinc indium sulfide material containing indium vacancies, showing an ideal distribution state.

[0037] 2. Compared with a single material, the nanoheterojunction prepared by the present invention exhibits a wide spectral absorption range from 350 nanometers to 800 nanometers, which significantly improves the utilization efficiency of visible light.

[0038] 3. The nano-heterojunction prepared by the present invention has excellent performance in photocurrent response, far exceeding that of a single material, and can effectively curb the recombination of photogenerated electrons and holes, thereby improving the carrier separation efficiency and electron transfer rate.

[0039] 4. Under visible light irradiation, the nanoheterojunction prepared by the present invention can achieve 99.8% efficient degradation of tetracycline in only 30 minutes. The degradation rates are 2.5 times and 1.6 times of those of porphyrin-based metal organic framework materials and zinc indium sulfide materials containing indium vacancies, respectively, demonstrating extremely high degradation efficiency.

[0040] 5. In practical applications, stability is a key indicator for measuring material performance. The nanoheterojunction prepared by the present invention exhibits excellent cyclic stability. Even after 5 rounds of degradation operations, its photocatalytic degradation rate can still be maintained at 98%, and the structure remains intact. In addition, the nanoheterojunction also has excellent environmental stability and can maintain good photocatalytic efficiency in both acidic and alkaline solutions, providing a strong guarantee for its application in complex water bodies. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The ultraviolet and visible light absorption spectra of the metal organic framework, zinc indium sulfide containing indium vacancies and nano heterojunction materials prepared by the present invention;

[0042] Figure 2 The photocurrent of the metal organic framework, zinc indium sulfide containing indium vacancies and nano heterojunction material prepared by the present invention;

[0043] Figure 3 The results are a comparison of the performance of the metal organic framework, zinc indium sulfide containing indium vacancies and nano-heterojunction materials prepared by the present invention in photocatalytic degradation of tetracycline;

[0044] Figure 4 It is the electron spin resonance spectrum of the nano heterojunction material prepared by the present invention under different time of irradiation in darkness or visible light;

[0045] Figure 5 The five-cycle experimental results of the nano-heterojunction material prepared by the present invention in the process of photocatalytic degradation of tetracycline;

[0046] Figure 6 It is an X-ray diffraction spectrum of the nano heterojunction material prepared by the present invention in five cycles of photocatalytic degradation of tetracycline. DETAILED DESCRIPTION

[0047] The contents of the present invention will be further explained below with reference to examples, but these examples do not limit the protection scope of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the protection scope of the present invention.

[0048] Example 1

[0049] (1) Preparation of nanoheterojunctions using solvothermal method:

[0050] Weigh 238 mg of Zn(NO3)2·6H2O, 565 mg of In(NO3)3·4H2O and 242 mg of cysteine ​​and mix with 60 mL of distilled water. Transfer the mixture to a 100 mL polytetrafluoroethylene autoclave, seal it and heat it at 160°C for 18 hours. After cooling, remove the supernatant, collect the black-green product by centrifugation, wash it with water and ethanol three times, and finally dry it in an oven at 80°C overnight to obtain zinc indium sulfide containing indium vacancies.

[0051] The synthesized zinc indium sulfide powder containing indium vacancies was uniformly dispersed in 10 mL N, N-dimethylformamide solution by ultrasonic treatment. Then, 10 mg of porphyrin ligand, 30 mg of ZrOCl2·8H2O and 280 mg of benzoic acid were added to the dispersion in sequence. The mixture was placed in an oil bath at 90°C and stirred for 5 hours. After the reaction, the obtained powder was collected by centrifugation, washed with ethanol 3 times, and then dried in an oven at 80°C to obtain a nano-heterojunction material of a metal organic framework PCN224 and zinc indium sulfide containing indium vacancies, with a yield of 70% to 80%.

[0052] (2) Research on the optical properties and photocurrent response of nano-heterojunction materials:

[0053] The metal organic framework, zinc indium sulfide containing indium vacancies and the nano-heterojunction materials composed of them were tested and analyzed by ultraviolet and visible absorption spectroscopy. Figure 1 As shown in the figure, compared with a single material, the nanoheterojunction exhibits a broad spectral absorption in the range of 350 to 800 nanometers, covering most of the ultraviolet to visible light. This shows that the formation of the nanoheterojunction significantly enhances the light absorption performance and broadens the light energy utilization range of the material. Subsequently, a photocurrent test was conducted to explore the separation efficiency of photogenerated electrons and holes. Figure 2 As shown, under the irradiation of intermittent visible light, the nanoheterojunction exhibited the highest photocurrent response, which strongly proved that it has excellent photogenerated carrier generation and transmission capabilities.

[0054] (3) Research on efficient photocatalytic degradation of tetracycline using nano-heterojunction materials:

[0055] In order to evaluate the photocatalytic performance of metal organic frameworks, indium vacancies-containing zinc indium sulfide and their nanoheterojunction materials, we conducted time-dependent degradation experiments of tetracycline. Figure 3As shown in the figure, under visible light irradiation, tetracycline hardly degrades without a catalyst; while the degradation rates of tetracycline by metal organic frameworks and zinc indium sulfide containing indium vacancies were 39.9% and 60.9%, respectively. In contrast, the nanoheterojunction showed the highest degradation efficiency, reaching a degradation rate of 99.8% under only 30 minutes of visible light irradiation, which is 2.5 times and 1.6 times that of metal organic frameworks and zinc indium sulfide containing indium vacancies, respectively. The test results of electron spin resonance spectroscopy further confirmed that the superoxide radicals produced by the activation of oxygen by the nanoheterojunction under light are the main active species for photodegradation of tetracycline ( Figure 4 ).

[0056] Stability is a key indicator to measure material performance. Figure 5 As shown in the figure, after 5 consecutive photocatalytic reactions, the nanoheterojunction can still maintain a good degradation effect and show good cycle stability. In addition, after 5 rounds of photocatalytic degradation, the X-ray diffraction pattern of the nanoheterojunction still shows good crystallinity ( Figure 6 ), confirming its feasibility as an efficient photocatalyst for the removal of tetracycline pollutants from wastewater.

[0057] Example 2

[0058] Preparation of nanoheterojunction materials containing single-atom iron.

[0059] Weigh 238 mg of Zn(NO3)2·6H2O, 565 mg of In(NO3)3·4H2O and 242 mg of cysteine ​​and mix with 60 mL of distilled water. Transfer the mixture to a 100 mL polytetrafluoroethylene autoclave, seal it and heat it at 160°C for 18 hours. After cooling, remove the supernatant, collect the black-green product by centrifugation, wash it with water and ethanol three times, and finally dry it in an oven at 80°C overnight to obtain zinc indium sulfide containing indium vacancies.

[0060] The synthesized zinc indium sulfide powder containing indium vacancies was uniformly dispersed in 10 mL N, N-dimethylformamide solution by ultrasonic treatment. Then, 10 mg of iron porphyrin ligand, 30 mg of ZrOCl2·8H2O and 280 mg of benzoic acid were added to the dispersion in sequence. The mixture was placed in an oil bath at 90°C and stirred for 5 hours. After the reaction, the obtained powder was collected by centrifugation, washed with ethanol three times, and then dried in an oven at 80°C to obtain a nano-heterojunction material of a metal organic framework PCN224 (Fe) and zinc indium sulfide containing indium vacancies.

[0061] Example 3

[0062] Preparation of nano-heterojunction materials containing single-atom copper.

[0063] Weigh 238 mg of Zn(NO3)2·6H2O, 565 mg of In(NO3)3·4H2O and 242 mg of cysteine ​​and mix with 60 mL of distilled water. Transfer the mixture to a 100 mL polytetrafluoroethylene autoclave, seal it and heat it at 160°C for 18 hours. After cooling, remove the supernatant, collect the black-green product by centrifugation, wash it with water and ethanol three times, and finally dry it in an oven at 80°C overnight to obtain zinc indium sulfide containing indium vacancies.

[0064] The synthesized zinc indium sulfide powder containing indium vacancies was uniformly dispersed in 10 mL N, N-dimethylformamide solution by ultrasonic treatment. Then, 10 mg of copper porphyrin ligand, 30 mg of ZrOCl2·8H2O and 280 mg of benzoic acid were added to the dispersion in sequence. The mixture was placed in an oil bath at 90°C and stirred for 5 hours. After the reaction, the obtained powder was collected by centrifugation, washed with ethanol three times, and then dried in an oven at 80°C to obtain a nano-heterojunction material of a metal organic framework PCN224 (Cu) and zinc indium sulfide containing indium vacancies.

[0065] Example 4

[0066] Preparation of nanoheterojunction materials containing single-atom palladium.

[0067] Weigh 238 mg of Zn(NO3)2·6H2O, 565 mg of In(NO3)3·4H2O and 242 mg of cysteine ​​and mix with 60 mL of distilled water. Transfer the mixture to a 100 mL polytetrafluoroethylene autoclave, seal it and heat it at 160°C for 18 hours. After cooling, remove the supernatant, collect the black-green product by centrifugation, wash it with water and ethanol three times, and finally dry it in an oven at 80°C overnight to obtain zinc indium sulfide containing indium vacancies.

[0068] The synthesized zinc indium sulfide powder containing indium vacancies was uniformly dispersed in 10 mL N, N-dimethylformamide solution by ultrasonic treatment. Then, 10 mg of palladium porphyrin ligand, 30 mg of ZrOCl2·8H2O and 280 mg of benzoic acid were added to the dispersion in sequence. The mixture was placed in an oil bath at 90°C and stirred for 5 hours. After the reaction, the obtained powder was collected by centrifugation, washed with ethanol three times, and then dried in an oven at 80°C to obtain a nano-heterojunction material of a metal organic framework PCN224 (Pd) and zinc indium sulfide containing indium vacancies.

[0069] Example 5

[0070] Preparation of nanoheterojunction materials containing single-atom platinum.

[0071] Weigh 238 mg of Zn(NO3)2·6H2O, 565 mg of In(NO3)3·4H2O and 242 mg of cysteine ​​and mix with 60 mL of distilled water. Transfer the mixture to a 100 mL polytetrafluoroethylene autoclave, seal it and heat it at 160°C for 18 hours. After cooling, remove the supernatant, collect the black-green product by centrifugation, wash it with water and ethanol three times, and finally dry it in an oven at 80°C overnight to obtain zinc indium sulfide containing indium vacancies.

[0072] The synthesized zinc indium sulfide powder containing indium vacancies was uniformly dispersed in 10 mL N, N-dimethylformamide solution by ultrasonic treatment. Then, 10 mg of platinum porphyrin ligand, 30 mg of ZrOCl2·8H2O and 280 mg of benzoic acid were added to the dispersion in sequence. The mixture was placed in an oil bath at 90°C and stirred for 5 hours. After the reaction, the obtained powder was collected by centrifugation, washed with ethanol three times, and then dried in an oven at 80°C to obtain a nano-heterojunction material of a metal organic framework PCN224 (Pt) and zinc indium sulfide containing indium vacancies.

[0073] Example 6

[0074] Preparation of nano-heterojunction materials containing single-atom manganese.

[0075] Weigh 238 mg of Zn(NO3)2·6H2O, 565 mg of In(NO3)3·4H2O and 242 mg of cysteine ​​and mix with 60 mL of distilled water. Transfer the mixture to a 100 mL polytetrafluoroethylene autoclave, seal it and heat it at 160°C for 18 hours. After cooling, remove the supernatant, collect the black-green product by centrifugation, wash it with water and ethanol three times, and finally dry it in an oven at 80°C overnight to obtain zinc indium sulfide containing indium vacancies.

[0076] The synthesized zinc indium sulfide powder containing indium vacancies was uniformly dispersed in 10 mL N, N-dimethylformamide solution by ultrasonic treatment. Then, 10 mg of manganese porphyrin ligand, 30 mg of ZrOCl2·8H2O and 280 mg of benzoic acid were added to the dispersion in sequence. The mixture was placed in an oil bath at 90°C and stirred for 5 hours. After the reaction, the obtained powder was collected by centrifugation, washed with ethanol three times, and then dried in an oven at 80°C to obtain a nano-heterojunction material of a metal organic framework PCN224 (Mn) and zinc indium sulfide containing indium vacancies.

Claims

1. A nano-heterojunction material for photodegradation of tetracycline, characterized in that: It is composed of a metal organic framework material and a zinc indium sulfide ternary semiconductor material containing indium vacancies; The zinc indium sulfide ternary semiconductor material containing indium vacancies is obtained by a solvothermal reaction of a metal nitrate comprising zinc nitrate and indium nitrate or a metal chloride comprising zinc chloride and indium chloride with a first organic ligand containing a mercapto group; The metal organic framework material is a metal organic framework material constructed with porphyrin or a porphyrin derivative as the second organic ligand.

2. The nano heterojunction material for photodegradation of tetracycline according to claim 1, characterized in that: The metal organic framework material is PCN224 or a functionalized derivative of PCN224.

3. The nano heterojunction material for photodegradation of tetracycline according to claim 1, characterized in that: The first organic ligand containing a thiol group is cysteine; The second organic ligand is at least one of porphyrin, iron porphyrin, copper porphyrin, palladium porphyrin, platinum porphyrin and manganese porphyrin.

4. The nano heterojunction material for photodegradation of tetracycline according to claim 3, characterized in that: When the raw material is metal nitrate, the mass ratio of zinc nitrate, indium nitrate and cysteine ​​is 1:2-3:1-2; When the raw material is a metal chloride, the mass ratio of zinc chloride, indium chloride and cysteine ​​is 1:3-4:2-3.

5. A method for preparing a nano heterojunction material for photodegradation of tetracycline, characterized in that: The following steps are involved: a) dissolving a metal nitrate or a metal chloride and a first organic ligand containing a thiol group in deionized water respectively, and obtaining a zinc indium sulfide material containing an indium vacancy by a solvothermal reaction; The metal nitrates include zinc nitrate and indium nitrate; the metal chlorides include zinc chloride and indium chloride; b) dispersing the zinc indium sulfide material containing indium vacancies obtained in step a) in an organic solvent, mixing it with a zirconium salt and a second organic ligand to carry out a solvothermal reaction, so as to obtain a nano-heterojunction material composite of a metal organic framework and zinc indium sulfide; The second organic ligand is porphyrin or a porphyrin derivative.

6. The method for preparing the nano heterojunction material for photodegradation of tetracycline according to claim 5, characterized in that: The first organic ligand containing a thiol group is cysteine; When the raw material is metal nitrate, the mass ratio of zinc nitrate, indium nitrate and cysteine ​​is 1:2-3:1-2; When the raw material is a metal chloride, the mass ratio of zinc chloride, indium chloride and cysteine ​​is 1:3-4:2-3.

7. The method for preparing the nano heterojunction material for photodegradation of tetracycline according to claim 5, characterized in that: In step b), the organic solvent is N,N-dimethylformamide; The zirconium salt is zirconium oxychloride; The second organic ligand is at least one of porphyrin, iron porphyrin, copper porphyrin, palladium porphyrin, platinum porphyrin and manganese porphyrin; The mass ratio of the zirconium salt to the second organic ligand is 3:

1.

8. The method for preparing the nano heterojunction material for photodegradation of tetracycline according to claim 5, characterized in that: In step a), the temperature of the solvent thermal reaction is 155 to 165° C. and the time is 16 to 18 hours; In step b), the temperature of the solvent thermal reaction is 85 to 95° C. and the time is 4 to 5 hours.

9. Use of the nano-heterojunction material for photodegradation of tetracycline according to any one of claims 1 to 4 in photocatalytic degradation of tetracycline.

10. A method for photocatalytic degradation of tetracycline, characterized in that: The nano heterojunction material for photodegradation of tetracycline according to any one of claims 1 to 4 is added to a water body contaminated by tetracycline, and then photocatalytic degradation is carried out to degrade the tetracycline.

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