Phosphorus-doped covalent triazine framework material as well as preparation method and application thereof

Abstract

The invention provides a phosphorus-doped covalent triazine framework material as well as a preparation method and application thereof, the phosphorus-doped covalent triazine framework material is synthesized from a covalent triazine framework material and sodium hypophosphite, and the mass ratio of the sodium hypophosphite to the covalent triazine framework material is (0.005-0.05): 1. According to the phosphorus-doped covalent triazine framework material as well as the preparation method and the application thereof provided by the invention, bisphenol A in water can be efficiently photocatalytically degraded.

Description

Technical Field

[0001] This invention belongs to the field of photocatalytic materials technology, specifically relating to a phosphorus-doped covalent triazine framework material, its preparation method, and its application. Background Technology

[0002] Bisphenol A (BPA) is an endocrine disruptor widely used in plastics production. During production and use, BPA inevitably enters the aquatic environment, posing a serious threat to aquatic ecosystems and human health. Even extremely low concentrations of BPA can interfere with the normal function of hormones in organisms, leading to reproductive and developmental abnormalities, sex imbalances, and decreased fertility in aquatic organisms such as fish and amphibians. Furthermore, due to its lipophilic and persistent nature, BPA easily accumulates in the fatty tissues of aquatic organisms and amplifies through the food chain, eventually entering the human body through aquatic products, causing endocrine disorders, reproductive problems, and even cancer. Therefore, BPA pollution has become a global aquatic environmental problem that urgently needs to be addressed.

[0003] BPA treatment and degradation technologies mainly include chemical oxidation, biological treatment, and adsorption / filtration. Chemical oxidation uses strong oxidants to generate free radicals that degrade BPA. Fenton-like processes and advanced oxidation processes (AOPs) are the most typical chemical oxidation methods, offering high efficiency, speed, and wide applicability, but they require the addition of oxidants and produce sludge. Biological treatment technologies utilizing microorganisms or enzymes to catalyze BPA decomposition are environmentally friendly, but have a long cycle time. Adsorption / filtration, as a physical method, shows good treatment effects in pretreatment or low-concentration scenarios, but it cannot fundamentally degrade BPA. Currently, photocatalytic degradation of BPA is attracting much attention due to its advantages such as not requiring the addition of oxidants, producing no sludge, and not being limited by microbial activity, making it a cutting-edge direction in BPA treatment. Currently, common photocatalysts for BPA degradation include TiO2, g-C3N4, sulfides, and metal-organic frameworks (MOFs). However, TiO2 only responds to ultraviolet light, resulting in low solar energy utilization; g-C3N4 and sulfide semiconductors have high carrier recombination rates, poor stability, and are prone to photocorrosion; metal-organic frameworks (MOFs) are cumbersome to synthesize, have poor stability, and are easily decomposed. Therefore, there is an urgent need for a photocatalyst with high stability and high efficiency to degrade BPA. Summary of the Invention

[0004] This invention provides a phosphorus-doped covalent triazine framework material, its preparation method, and its application, which can efficiently photocatalytically degrade bisphenol A in water.

[0005] To address the aforementioned technical problems, embodiments of the present invention provide a phosphorus-doped covalent triazine framework material, synthesized from a covalent triazine framework material and sodium hypophosphite, wherein the mass ratio of sodium hypophosphite to the covalent triazine framework material is 0.005 to 0.05:1.

[0006] As a further improvement to the embodiments of the present invention, the following steps are included: Step 10: Prepare a covalent triazine framework material; Step 20: Phosphorus-doped covalent triazine framework material is synthesized by combining covalent triazine framework material and sodium hypophosphite.

[0007] As a further improvement to this embodiment of the invention, step 20 specifically includes: Step 201: Mix and grind the covalent triazine framework material and sodium hypophosphite; Step 202: Place the ground mixture into a covered crucible, and place the crucible into a muffle furnace and heat it to a preset temperature; Step 203: After maintaining the preset time, cool to room temperature; Step 204: The obtained powder is washed and dried under vacuum to obtain a phosphorus-doped covalent triazine framework material.

[0008] As a further improvement of this embodiment of the invention, the mass ratio of sodium hypophosphite to covalent triazine framework material is 0.005 to 0.05:1.

[0009] As a further improvement of this embodiment of the invention, the preset temperature is 200-400℃.

[0010] As a further improvement to this embodiment of the invention, in step 202, the temperature is heated to a preset temperature at a heating rate of 2 to 20°C / min.

[0011] As a further improvement to this embodiment of the invention, in step 202, the crucible is filled with inert gas.

[0012] As a further improvement of the present invention, the phosphorus-doped covalent triazine framework material is used for photocatalytic degradation of bisphenol A.

[0013] Compared with the prior art, the technical solution of the present invention has the following beneficial effects: This invention provides a phosphorus-doped covalent triazine framework material, its preparation method, and its application. Phosphorus-doped covalent triazine framework materials (P-CTFs) are synthesized using covalent triazine framework materials and sodium hypophosphite. The in-plane π-conjugated structure of the covalent triazine framework material (CTFs) facilitates visible light absorption, and the orderly stacking of layers through π-π interactions promotes the migration of photogenerated carriers. As the reaction temperature increases, sodium hypophosphite decomposes to produce reducing PH3 gas. PH3 can reduce the local structure of CTFs, causing partial structural damage and defects, allowing phosphorus atoms to be doped into the CTF framework structure. P-atom doping not only modulates the band structure of CTFs but also promotes carrier separation and migration, significantly improving the performance of photocatalytic oxidation degradation of bisphenol A. This invention uses sodium hypophosphite as the phosphorus source, which has high activity and a low decomposition temperature, allowing it to react with the covalent triazine framework material at a lower temperature. At this lower temperature, the CTFs can maintain their original framework structure, avoiding overall structural damage that would affect the migration of photogenerated carriers. Attached Figure Description

[0014] Figure 1 The image shows the X-ray diffraction pattern of the P-CTFs prepared in Example 2. Detailed Implementation

[0015] The technical solution of the present invention will now be described in detail with reference to the accompanying drawings.

[0016] This invention provides a phosphorus-doped covalent triazine framework material, synthesized from a covalent triazine framework material and sodium hypophosphite, wherein the mass ratio of sodium hypophosphite to covalent triazine framework material is 0.005 to 0.05:1.

[0017] In this invention, sodium hypophosphite is used as the phosphorus source to synthesize phosphorus-doped covalent triazine framework materials. Sodium hypophosphite has high activity and a low decomposition temperature, which can generate PH3 gas at a lower temperature. The PH3 gas reduces the local structure of CTFs, and some structures are destroyed, resulting in defects. Thus, phosphorus atoms are doped into the CTF framework structure, promoting the separation and migration of charge carriers and improving photocatalytic degradation performance. At the same time, at a lower temperature, CTFs can maintain their original framework structure, avoiding the destruction of the overall structure and affecting the migration of photogenerated charge carriers. Sodium hypophosphite and covalent triazine framework materials are synthesized with an appropriate mass ratio to ensure that a certain amount of phosphorus atoms are doped into the CTF framework structure, while also preventing excessive PH3 gas from promoting the ring-opening decomposition of P-CTFs and reducing photocatalytic degradation performance.

[0018] This invention also provides a method for preparing a phosphorus-doped covalent triazine framework material, comprising the following steps: Step 10: Prepare a covalent triazine framework material.

[0019] The embodiments of the present invention use existing methods to prepare covalent triazine framework materials CTFs.

[0020] Step 20: Phosphorus-doped covalent triazine framework material is synthesized by combining covalent triazine framework material and sodium hypophosphite.

[0021] Specifically, it includes: Step 201: Mix and grind the covalent triazine framework material and sodium hypophosphite.

[0022] Preferably, the mass ratio of sodium hypophosphite to covalent triazine framework material is 0.005 to 0.05:1.

[0023] Step 202: Place the ground mixture into a covered crucible and place the crucible into a muffle furnace and heat it to a preset temperature.

[0024] Preferably, the crucible is filled with an inert gas, such as nitrogen or argon, to ensure that there is no oxygen in the reaction system and to prevent the covalent triazine framework material from being oxidized and ignited.

[0025] Preferably, the temperature is heated to the preset temperature at a heating rate of 2–20 °C / min. If the heating rate is too fast, the sodium hypophosphite will decompose too quickly and completely in a short time. This will result in the generated PH3 not reacting sufficiently with the covalent triazine framework material, leading to a decrease in P doping. If the heating rate is too slow, the sodium phosphate will decompose first, but may not have reached the temperature required to react with the covalent triazine framework material, which will also result in insufficient P doping.

[0026] Preferably, the preset temperature is 200–400℃. If the reaction temperature is too high, the covalent triazine framework material will decompose, and the structure will be significantly damaged. If the temperature is too low, the reaction between PH3 and the covalent triazine framework material will be insufficient, and the phosphorus element cannot be effectively introduced into the framework.

[0027] Step 203: After maintaining the preset time, cool to room temperature.

[0028] Step 204: The obtained powder is washed multiple times with ethanol and deionized water and dried under vacuum to obtain phosphorus-doped covalent triazine framework materials P-CTFs.

[0029] This invention also provides an application of the phosphorus-doped covalent triazine framework material provided in the above embodiments, which is used for photocatalytic degradation of bisphenol A.

[0030] Specifically, an appropriate amount of phosphorus-doped covalent triazine framework material was added to a BPA aqueous solution, ultrasonically vibrated until homogeneous, and then stirred under light-protected conditions to achieve solid-liquid adsorption equilibrium. Degradation was then carried out under illumination from a reaction light source (300 W xenon lamp, λ≥420 nm).

[0031] After the degradation reaction, the reaction solution was taken, the supernatant was collected by centrifugation, and its absorbance was measured at 275 nm using a UV-Vis spectrophotometer to obtain the degradation rate of BPA.

[0032] The following examples and comparative examples illustrate the performance of the phosphorus-doped covalent triazine framework material synthesized in this invention.

[0033] Example 1 Weigh 9.6 g (40.00 mmol) of terephthalamide hydrochloride and 20.00 g of cesium carbonate and add them to 400.0 mL of dimethyl sulfoxide. Heat to 100 °C and stir for 0.5 h. Add 200.0 mL of dimethyl sulfoxide solution containing 2.8 g (20.00 mmol) of terephthalaldehyde to the above solution at a rate of 0.5 mL / h. Continue to maintain the temperature at 100 °C for 12 h, then raise the temperature to 160 °C and maintain it for 36 h. Centrifuge to separate the precipitate formed by the reaction, and then wash successively with 1.00 mol / L hydrochloric acid, deionized water, ethanol and tetrahydrofuran. Dry under vacuum at 80 °C to obtain 8.6 g of yellow CTF solid product.

[0034] Weigh 0.40 g of CTFs and 2 mg of NaH2PO2, grind and mix them, place them in a covered crucible filled with argon gas, and place the crucible in a muffle furnace. Heat the mixture to 300 °C at a heating rate of 10 °C / min and maintain the temperature for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.34 g of P-CTFs.

[0035] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 89.2%.

[0036] Example 2 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 10 mg of NaH2PO2. Place the mixture in a covered crucible filled with argon gas. Put the crucible in a muffle furnace and heat it to 300 °C at a heating rate of 10 °C / min, and hold for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.31 g of P-CTFs.

[0037] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 97.9%.

[0038] Example 3 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 20 mg of NaH2PO2. Place the mixture in a covered crucible filled with argon gas. Put the crucible in a muffle furnace and heat it to 300 °C at a heating rate of 10 °C / min, and hold for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.27 g of P-CTFs.

[0039] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonication to homogenize, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 98.4%.

[0040] Example 4 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 10 mg of NaH2PO2. Place the mixture in a covered crucible filled with nitrogen gas. Put the crucible in a muffle furnace and heat it to 300 °C at a heating rate of 10 °C / min, and hold for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.32 g of P-CTFs.

[0041] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 96.4%.

[0042] Example 5 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 10 mg of NaH2PO2. Place the mixture in a covered crucible filled with nitrogen gas. Put the crucible in a muffle furnace and heat it to 300 °C at a heating rate of 2 °C / min, and hold for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.3 g of P-CTFs.

[0043] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonication to homogenize, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 86.9%.

[0044] Example 6 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 10 mg of NaH2PO2. Place the mixture in a covered crucible filled with nitrogen gas. Put the crucible in a muffle furnace and heat it to 300 °C at a heating rate of 20 °C / min, and hold for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.30 g of P-CTFs.

[0045] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 75.5%.

[0046] Example 7 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 10 mg of NaH2PO2. Place the mixture in a covered crucible filled with nitrogen gas. Put the crucible in a muffle furnace and heat it to 200 °C at a heating rate of 10 °C / min, and maintain the temperature for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.31 g of P-CTFs.

[0047] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was collected every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 71%.

[0048] Example 8 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 10 mg of NaH2PO2. Place the mixture in a covered crucible filled with nitrogen gas. Put the crucible in a muffle furnace and heat it to 400 °C at a heating rate of 10 °C / min, and hold for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.22 g of P-CTFs.

[0049] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 38.4%.

[0050] Comparative Example 1 20 mg of the CTFs prepared in Example 1 was weighed and placed in 50 mL of a 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 15.8%.

[0051] Comparative Example 2 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 30 mg of NaH2PO2. Place the mixture in a covered crucible filled with nitrogen gas. Put the crucible in a muffle furnace and heat it to 300 °C at a heating rate of 10 °C / min, and hold for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.27 g of P-CTFs.

[0052] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was taken every 15 min, centrifuged, and the supernatant was collected. The absorbance of the supernatant was measured at 275 nm using a UV-Vis spectrophotometer. After 2 hours, the degradation rate of BPA was 71.7%.

[0053] Comparative Example 3 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 10 mg of NaH2PO2. Place the mixture in a covered crucible filled with nitrogen gas. Put the crucible in a muffle furnace and heat it to 300 °C at a heating rate of 50 °C / min, and maintain the temperature for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.23 g of P-CTFs.

[0054] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. The degradation experiment was then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was collected every 15 min, centrifuged, and the supernatant was measured using a UV-Vis spectrophotometer at 275 nm. After 2 hours, the degradation rate of BPA was 66.1%.

[0055] Comparative Example 4 Weigh 0.40 g of the CTFs prepared in Example 1 and grind and mix them with 10 mg of NaH2PO2. Place the mixture in a covered crucible filled with nitrogen gas. Put the crucible in a muffle furnace and heat it to 500 °C at a heating rate of 10 °C / min, and hold for 1 h. After cooling to room temperature, wash the obtained powder sample several times with ethanol and deionized water, and dry it under vacuum at 50 °C for 24 h to obtain 0.19 g of P-CTFs.

[0056] 20 mg of P-CTFs were weighed and placed in 50 mL of 20 mg / L BPA aqueous solution. After ultrasonic agitation, the mixture was stirred for 30 min under light-protected conditions to allow the reaction system to reach solid-liquid adsorption equilibrium. Degradation experiments were then conducted under illumination from a 300 W xenon lamp (λ≥420 nm). 1 mL of solution was collected every 15 min, centrifuged, and the supernatant was measured using a UV-Vis spectrophotometer at 275 nm. After 2 hours, the degradation rate of BPA was 6.8%.

[0057] The P-CTFs synthesized in Example 2 were detected using an X-ray diffractometer, and the results were as follows: Figure 1 The graph shown shows that the synthesized P-CTFs have high crystallinity, indicating that the framework structure of the CTFs can still be maintained after doping with P atoms using this method.

[0058] As can be seen from the comparison between Comparative Example 1 and all examples, the P-CTFs prepared in the examples of this invention have a much better catalytic effect than CTFs. According to Examples 1, 2, and 3, the catalytic effect of P-CTFs gradually increases with the increasing proportion of sodium hypophosphite. However, according to Comparative Example 2, if the proportion of sodium hypophosphite is too high, the catalytic effect of P-CTFs decreases. Comparing Examples 2 and 3, it can be seen that if the heating rate is too fast, the catalytic effect of P-CTFs will decrease. Comparing Examples 2 and 4, it can be seen that if the temperature is too high, the catalytic effect of P-CTFs will decrease.

[0059] In this invention, sodium hypophosphite is used as a phosphorus source to synthesize a phosphorus-doped covalent triazine framework material. By using an appropriate mass ratio of sodium hypophosphite to covalent triazine framework material and heating to a suitable temperature at an appropriate heating rate, the resulting phosphorus-doped covalent triazine framework material exhibits excellent photocatalytic performance and can achieve a high degradation rate when used for photocatalytic degradation of bisphenol A.

[0060] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A phosphorus-doped covalent triazine framework material, characterized in that, It is synthesized from a covalent triazine framework material and sodium hypophosphite, with a mass ratio of sodium hypophosphite to covalent triazine framework material of 0.005 to 0.05:

1.

2. A method for preparing a phosphorus-doped covalent triazine framework material, characterized in that, Includes the following steps: Step 10: Prepare a covalent triazine framework material; Step 20: Phosphorus-doped covalent triazine framework material is synthesized by combining covalent triazine framework material and sodium hypophosphite.

3. The preparation method according to claim 2, characterized in that, Step 20 specifically includes: Step 201: Mix and grind the covalent triazine framework material and sodium hypophosphite; Step 202: Place the ground mixture into a covered crucible, and place the crucible into a muffle furnace and heat it to a preset temperature; Step 203: After maintaining the preset time, cool to room temperature; Step 204: The obtained powder is washed and dried under vacuum to obtain a phosphorus-doped covalent triazine framework material.

4. The preparation method according to claim 3, characterized in that, The mass ratio of sodium hypophosphite to covalent triazine framework material is 0.005 to 0.05:

1.

5. The preparation method according to claim 3, characterized in that, The preset temperature is 200–400°C.

6. The preparation method according to claim 3, characterized in that, In step 202, the temperature is increased to the preset temperature at a heating rate of 2 to 20°C / min.

7. The preparation method according to claim 3, characterized in that, In step 202, the crucible is filled with inert gas.

8. An application of the phosphorus-doped covalent triazine framework material according to claim 1, characterized in that, The phosphorus-doped covalent triazine framework material is used for the photocatalytic degradation of bisphenol A.

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