A photocatalytic self-fenton water treatment method based on graphene oxide / self-assembled carboxyl-containing perylene imide

Abstract

The application belongs to the technical field of environmental material preparation, and relates to application of a photocatalytic self-Fenton water treatment method based on graphene oxide / self-assembled carboxyl-containing perylene diimide (GO / SA-PDI). Self-assembled carboxyl-containing perylene diimide (SA-PDI) is prepared by a supramolecular self-assembly method, and a GO / SA-PDI composite photocatalyst is prepared by a low-temperature hydrothermal method; then, Fe salt and the photocatalyst are added to a reaction system to construct a photocatalytic self-Fenton system for water treatment. The GO introduced in the prepared GO / SA-PDI can effectively enhance the light absorption capacity, increase the number of surface active sites, and accelerate the separation and migration rate of photo-generated charges, thereby improving the ability of the GO / SA-PDI to in-situ synthesize H2O2 by reducing O2 through photo-generated electrons. The disclosed photocatalytic self-Fenton water treatment method based on GO / SA-PDI can generate a large number of hydroxyl radicals and photo-generated holes to enhance the oxidation capacity and mineralization efficiency of the synergistic reaction system, thereby realizing efficient removal of antibiotics, drug-resistant bacteria and resistance genes in water.

Description

Technical Field

[0001] This invention relates to a photocatalytic self-Fenton water treatment method based on graphene oxide / self-assembled carboxylated perylene imide (GO / SA-PDI), belonging to the fields of environmental chemistry and materials science. Background Technology

[0002] Antibiotics, used to prevent and treat infections caused by pathogenic bacteria, are widely used in the medical, livestock, and aquaculture industries. However, once antibiotics enter the human or animal body, they cannot be completely metabolized and are discharged into the environment through industrial, hospital, household, and livestock wastewater. Due to their environmental persistence, biotoxicity, and bioaccumulation, they seriously impact public health and ecosystems. More seriously, long-term accumulation of antibiotics can induce antibiotic-resistant bacteria (ARBs) and antibiotic resistance genes (ARGs), accelerating the spread and diffusion of antibiotic resistance. ARBs can enter farmed organisms and humans through the food chain, leading to outbreaks and epidemics of various diseases. ARGs can migrate and transform in the aquatic environment through horizontal and vertical gene transfer, making the spread of antibiotic resistance more widespread and rapid. Therefore, developing deep treatment technologies for the efficient removal of antibiotics, ARBs, and ARGs from the aquatic environment is of great significance for controlling antibiotic resistance pollution.

[0003] Photocatalytic self-Fenton oxidation is an emerging advanced oxidation technology that couples photocatalysis with Fenton oxidation. It primarily utilizes a photocatalyst to efficiently produce H₂O₂ in situ, then promotes a heterogeneous self-Fenton reaction via iron-mediated processes, achieving "self-production and self-use" of H₂O₂ and converting it into a large amount of hydroxyl radicals (·OH), significantly enhancing the oxidation capacity of the reaction system. Furthermore, the reducing power of the electrons generated by the photocatalyst can promote the Fe... 3+ / Fe 2+ The self-Fenton photocatalytic system improves the utilization rate of H2O2 through cyclic conversion, while inhibiting the recombination of photogenerated electron-hole pairs and releasing more free photogenerated holes, further enhancing the mineralization efficiency of the reaction system. Thus, without adding external H2O2, a photocatalytic self-Fenton synergistic system with strong oxidizing power and high mineralization efficiency is constructed, resulting in a more significant mineralization removal effect on antibiotics, drug-resistant bacteria, and resistance genes in water. However, current photocatalytic self-Fenton technology still faces practical problems such as low conversion efficiency of the photocatalyst to solar energy and insufficient number of photogenerated electrons in the reaction system, limiting its application prospects. Summary of the Invention

[0004] Self-assembled carboxylic acid perylene diimide (SA-PDI) photocatalysts possess advantages such as a wide visible light response range, diverse elemental sources, easily tunable structure, and high stability. They are widely used in fields such as organic matter degradation, pathogenic bacteria elimination, photocatalytic water splitting for oxygen production, and H2O2 synthesis, making them suitable supports for constructing photocatalytic self-Fenton synergistic reaction systems. However, SA-PDI particles prepared by supramolecular self-assembly are small in size and prone to aggregation, resulting in a high recombination probability of photogenerated electron-hole pairs, which affects their photocatalytic activity. Loading SA-PDI photocatalysts onto graphene oxide (GO) with a two-dimensional nanosheet structure is a feasible modification strategy. GO's high light absorption can improve the light absorption capacity of SA-PDI, GO's two-dimensional nanosheet structure and high specific surface area can promote the uniform dispersion of SA-PDI, thereby exposing more active sites, and GO's high conductivity can improve the separation and migration rates of photogenerated charge carriers in SA-PDI. Therefore, introducing GO into the SA-PDI system can further improve its photocatalytic activity, making it more in line with the requirements for constructing a photocatalytic self-Fenton reaction system, which is the key to solving the problem.

[0005] To address the problems existing in the prior art, this invention prepares a GO / SA-PDI composite photocatalyst via a low-temperature hydrothermal method; then, by adding Fe salt to the reaction system, a photocatalytic self-Fenton water treatment method based on GO / SA-PDI is developed. The introduction of GO into the GO / SA-PDI prepared in this invention effectively enhances its light absorption capacity, increases the number of surface active sites, and accelerates the separation and migration rate of photogenerated charges, thereby improving the ability of GO / SA-PDI to synthesize H2O2 in situ through the reduction of O2 by photogenerated electrons, thus solving the problems existing in current SA-PDI photocatalysts and photocatalytic self-Fenton technology. Compared to the photocatalytic system, the synergistic effect of GO / SA-PDI in the photocatalytic self-Fenton system is improved. The high light absorption of GO is beneficial to improving the solar energy conversion efficiency of the catalyst, thereby generating more photogenerated electrons to participate in the reduction of Fe. 3+ In the reaction, the negative surface charge of GO is beneficial to improving the catalyst's response to Fe. 2+ and Fe 3+ The adsorption capacity of cations accelerates the self-Fenton reaction, and the high conductivity of GO also helps to increase the transfer rate of photogenerated electrons in the catalyst, thereby accelerating the reduction of Fe by photogenerated electrons. 3+ The reaction progresses, thereby increasing the Fe content in the cooperative reaction system. 3+ / Fe 2+ The recycling rate and H2O2 utilization rate further improve the oxidation capacity and mineralization efficiency of the photocatalytic self-Fenton system.

[0006] The purpose of this invention is to provide a photocatalytic self-Fenton water treatment method based on graphene oxide / self-assembled carboxylic perylene imide.

[0007] The water treatment method is as follows: graphene oxide / self-assembled carboxyl perylene imide photocatalyst is added to the wastewater to be treated, the pH and temperature of the reaction system are adjusted, Fe salt is added to the reaction system to construct a photocatalytic self-Fenton system, the reaction system is placed under a light source for irradiation, and continuous aeration is carried out to keep the solution in an oxygen-saturated state.

[0008] The preparation method of the graphene oxide / self-assembled carboxyl perylene imide is as follows:

[0009] Step 1: 3,4,9,10-perylenetetracarboxylic acid dianhydride, imidazole and β-aminopropionic acid are mixed and heated and stirred under inert gas protection. Then alcohol and acid solution are added and stirred. After the reaction is completed, the mixture is separated, purified, dried and ground to prepare carboxyl perylene imide.

[0010] Step 2: Disperse carboxylated perylene imide in water, add amine compounds, heat and stir until the solid is completely dissolved, add acid solution, heat and stir until precipitation stops, thus preparing a self-assembled carboxylated perylene imide dispersion, i.e., SA-PDI dispersion; the mass-to-volume ratio of carboxylated perylene imide to water is 1:0.05–20 mg / mL; the mass-to-volume ratio of carboxylated perylene imide to amine compounds is 1:0.05–20 mg / μL; the concentration of the acid solution is 0.01–18 mol / L; the mass-to-volume ratio of carboxylated perylene imide to acid solution is 1:0.005–2 mg / mL.

[0011] Step 3: Prepare graphene oxide dispersion, i.e. GO dispersion;

[0012] Step 4: Mix SA-PDI dispersion and GO dispersion. The mass ratio of graphene oxide to self-assembled carboxylated perylene imide is 1:0.1-1000. The mixture is subjected to ultrasonic treatment, followed by heating and stirring. After the reaction is completed, the mixture is separated, purified, dried, and ground to prepare graphene oxide / self-assembled carboxylated perylene imide, which is GO / SA-PDI photocatalyst.

[0013] In one embodiment, the GO / SA-PDI photocatalyst is added to the wastewater to be treated and then ultrasonically dispersed. The ultrasonic power is 200-800W, the ultrasonic frequency is 10-50kHz, and the ultrasonic time is 0.1-10h.

[0014] In one embodiment, the mass ratio of GO / SA-PDI photocatalyst to Fe salt is 1:0.005-20, the pH of the reaction system is 1-14, and the reaction temperature is 0-100℃.

[0015] In one embodiment, the mass ratio of GO / SA-PDI photocatalyst to Fe salt is less than 5:4.

[0016] In one embodiment, the mass ratio of GO / SA-PDI photocatalyst to Fe salt is 5:2.

[0017] In one embodiment, the pH of the reaction system is 5 to 8.

[0018] In one embodiment, the Fe salt includes ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, or ferrous sulfate.

[0019] The introduced gas includes oxygen, air, or a mixture of oxygen and argon, and the gas flow rate is 0.1 to 10 mL / min;

[0020] Light sources include LED lamps, xenon lamps, high-pressure mercury lamps, metal halide lamps, or sunlight.

[0021] In one embodiment, after adjusting the pH and temperature of the reaction system, the mixture is stirred to reach adsorption-desorption equilibrium. The stirring speed is 50–1500 r / min, and the stirring time is 0.1–10 h.

[0022] In one embodiment, step 1 of the method for preparing graphene oxide / self-assembled carboxyl-containing perylene imide includes:

[0023] The mass ratio of 3,4,9,10-perylenetetracarboxylic acid dianhydride to β-aminopropionic acid is 1:0.1 to 10;

[0024] The mass ratio of 3,4,9,10-perylenetetracarboxylic acid dianhydride to imidazole is 1:0.1 to 50;

[0025] The mass-to-volume ratio of the 3,4,9,10-perylenetetracarboxylic acid dianhydride to the alcohol is 1:1 to 200 g / mL;

[0026] The mass-to-volume ratio of the 3,4,9,10-perylenetetracarboxylic acid dianhydride to the acid solution is 1:1 to 1000 g / mL, and the concentration of the acid solution is 0.01 to 18 mol / L.

[0027] The heating temperature is 80–150°C;

[0028] The stirring speed is 50–1500 r / min, and the stirring time is 0.1–30 h;

[0029] The separation and purification process includes centrifugation followed by precipitate washing; the centrifugation speed is 1000–15000 r / min;

[0030] The drying method is atmospheric pressure drying, vacuum drying or freeze drying, the drying temperature is 0 to 100°C, the drying time is 1 to 50 hours, and the grinding time is 0.1 to 10 hours.

[0031] In one embodiment, step 1 of the method for preparing graphene oxide / self-assembled carboxyl-containing perylene imide includes:

[0032] The inert gas mentioned includes argon, nitrogen, or helium;

[0033] The alcohols mentioned include ethanol, methanol, or isopropanol;

[0034] The acid solution includes hydrochloric acid, nitric acid, or sulfuric acid solution.

[0035] In one embodiment, step 2 of the method for preparing graphene oxide / self-assembled carboxyl-containing perylene imide includes:

[0036] The heating temperature is 30–100°C;

[0037] The stirring speed is 50–1500 r / min, and the stirring time is 0.1–10 h;

[0038] The rate at which the acid solution is added is 0.1–100 mL / min.

[0039] In one embodiment, step 2 of the method for preparing graphene oxide / self-assembled carboxyl-containing perylene imide includes:

[0040] The amine compound is triethylamine, ethylenediamine, or tripropylamine;

[0041] The acid solution includes hydrochloric acid, nitric acid, or sulfuric acid solution.

[0042] In one embodiment, step 3 of the method for preparing graphene oxide / self-assembled carboxylic perylene imide involves: obtaining a GO dispersion by dispersing graphene oxide in water and then ultrasonicating it.

[0043] The mass-to-volume ratio of the oxidized graphite to water (mg / mL) is 1:0.01 to 100;

[0044] The ultrasonic power is 200–800W, the ultrasonic frequency is 10–50kHz, and the ultrasonic time is 0.1–10h.

[0045] In one embodiment, step 4 of the method for preparing graphene oxide / self-assembled carboxyl-containing perylene imide includes:

[0046] The ultrasonic power is 200–800W, the ultrasonic frequency is 10–50kHz, and the ultrasonic time is 0.1–10h.

[0047] The heating temperature is 30–100°C;

[0048] The stirring speed is 50–1500 r / min, and the stirring time is 0.1–10 h;

[0049] The separation and purification process includes centrifugation followed by precipitate washing; the centrifugation speed is 1000–15000 r / min;

[0050] The drying method is atmospheric pressure drying, vacuum drying or freeze drying, the drying temperature is 0 to 100°C, the drying time is 1 to 50 hours, and the grinding time is 0.1 to 10 hours.

[0051] In one embodiment, the mass ratio of graphene oxide to self-assembled carboxyl perylene imide is 1:(1-20).

[0052] In one embodiment, the mass ratio of graphene oxide to self-assembled carboxylated perylene imide is 1:19.

[0053] In one embodiment, the mass ratio of graphene oxide to self-assembled carboxylated perylene imide is 1:10.

[0054] In one embodiment, the mass ratio of graphene oxide to self-assembled carboxylated perylene imide is 1:4.

[0055] In one embodiment, the mass ratio of graphene oxide to self-assembled carboxylated perylene imide is 3:7.

[0056] In one embodiment, the mass ratio of graphene oxide to self-assembled carboxylated perylene imide is 2:3.

[0057] In one embodiment, the mass ratio of graphene oxide to self-assembled carboxylated perylene imide is 1:1.

[0058] The aforementioned photocatalytic self-Fenton water treatment method based on graphene oxide / self-assembled carboxylic acid perylene imide is used to remove one or more of sulfonamide antibiotics, quinolone antibiotics, and tetracycline antibiotics, one or more of sulfonamide-resistant bacteria, quinolone-resistant bacteria, and tetracycline-resistant bacteria, and one or more of sulfonamide resistance genes, quinolone resistance genes, and tetracycline resistance genes from water.

[0059] Beneficial effects:

[0060] (1) The GO / SA-PDI photocatalyst prepared in this invention has superior performance in synthesizing H2O2, degrading organic matter, killing drug-resistant bacteria and removing resistance genes compared with the SA-PDI photocatalyst.

[0061] (2) The photocatalytic self-Fenton water treatment method based on GO / SA-PDI developed in this invention has superior performance in degrading organic matter, killing drug-resistant bacteria and removing resistance genes compared with Fenton alone and photocatalytic water treatment methods.

[0062] (3) The method described in this invention has mild reaction conditions, simple process, high versatility and good stability, and is a green and efficient new water treatment technology.

[0063] This invention prepares a GO / SA-PDI composite photocatalyst via a low-temperature hydrothermal method. On one hand, the introduction of GO promotes the uniform dispersion of SA-PDI particles on the surface of its two-dimensional nanosheets, thereby exposing more active sites, increasing surface activity, and enhancing the composite photocatalyst's adsorption capacity for O2 and pollutants. This accelerates the reaction in which photogenerated charges participate in the synthesis of H2O2 and the removal of pollutants. The introduction of GO also enhances the light absorption capacity of the composite photocatalyst, leading to the generation of more photogenerated charges participating in the reaction. GO, as an electron acceptor, can improve the separation and migration rate of photogenerated charges in the composite photocatalyst, effectively suppressing the recombination probability of electron-hole pairs, thus significantly improving the ability of the GO / SA-PDI composite photocatalyst to synthesize H2O2 in situ through photogenerated electron reduction of O2, degrade organic matter, kill drug-resistant bacteria, and remove resistance genes. On the other hand, this invention constructs a GO / SA-PDI-based photocatalytic self-Fenton synergistic system by adding Fe salt to the GO / SA-PDI reaction system. Photogenerated electrons can promptly convert Fe... 3+ Reduced to Fe 2+ Promote Fe 3+ / Fe 2+ The cyclic conversion significantly improves the in-situ production of H2O2 and Fe by GO / SA-PDI. 2+ The efficiency of generating ·OH through the self-Fenton reaction further enhances the oxidation capacity of the reaction system. Simultaneously, the consumption of photogenerated electrons successfully suppresses the recombination of its own photogenerated charges, releasing more free photogenerated holes to participate in the oxidation reaction, further enhancing the mineralization efficiency of the reaction system. Under the synergistic effect of a large amount of ·OH and photogenerated holes, the GO / SA-PDI-based photocatalytic self-Fenton water treatment method achieves highly efficient removal of organic matter, ARBs, and ARGs from water. Therefore, this invention develops a GO / SA-PDI-based photocatalytic self-Fenton water treatment method with strong oxidation capacity and high mineralization efficiency without the addition of H2O2, achieving better environmental purification effects and higher application value than Fenton and photocatalytic water treatment methods alone. Attached Figure Description

[0064] Figure 1 The table shows a comparison of the H2O2 synthesis performance of GO / SA-PDI prepared in Examples 1-6 with SA-PDI prepared in Comparative Example 1, g-C3N4 prepared in Comparative Example 3, GO / SA-PDI (80%) (physical mixing) prepared in Comparative Example 4, carboxyl perylene imide / oxygen-doped carbon nitride nanosheets prepared in Comparative Example 5, and cobalt-embedded nitrogen-rich porous carbon material / self-assembled carboxyl perylene imide prepared in Comparative Example 6.

[0065] Figure 2 The graph shows a comparison of the degradation performance of sulfamethoxazole by the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) prepared in Example 1 under different conditions; where (a) under different types of Fe salts, (b) under different amounts of Fe salts added, and (c) under different pH conditions.

[0066] Figure 3 The graph shows a comparison of the degradation rates of sulfamethoxazole and its total organic carbon (TOC) by the photocatalytic water treatment method based on GO / SA-PDI (80%) prepared in Example 1, the photocatalytic water treatment method based on SA-PDI prepared in Comparative Example 1, the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7, the photocatalytic self-Fenton water treatment method based on SA-PDI in Comparative Example 7, and the Fenton water treatment method in Comparative Example 8. Among them, (a) degradation activity curve, (b) apparent rate constant, and (c) TOC removal rate.

[0067] Figure 4 This is a cyclic degradation activity diagram of the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7.

[0068] Figure 5 The graph shows a comparison of the photocatalytic water treatment performance of the GO / SA-PDI (80%) prepared in Example 1, the photocatalytic water treatment method based on SA-PDI prepared in Comparative Example 1, the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7, the photocatalytic self-Fenton water treatment method based on SA-PDI in Comparative Example 7, and the Fenton water treatment method in Comparative Example 8 in killing sulfonamide ARBs.

[0069] Figure 6 The graph shows a comparison of the photocatalytic water treatment methods based on GO / SA-PDI (80%) prepared in Example 1, the photocatalytic water treatment methods based on SA-PDI prepared in Comparative Example 1, the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7, the photocatalytic self-Fenton water treatment method based on SA-PDI in Comparative Example 7, and the Fenton water treatment method in Comparative Example 8 in terms of the removal performance of sulfonamide ARGs.

[0070] Figure 7 TEM comparison images of GO / SA-PDI (80%) prepared in Example 1, SA-PDI prepared in Comparative Example 1, and GO prepared in Comparative Example 2; wherein, (a) GO, (b) SA-PDI and (c) GO / SA-PDI (80%) are TEM images.

[0071] Figure 8The XRD patterns are comparison images of GO / SA-PDI prepared in Examples 1-6 with SA-PDI prepared in Comparative Example 1 and GO prepared in Comparative Example 2.

[0072] Figure 9 Raman comparison diagrams of GO / SA-PDI (80%) prepared in Example 1, SA-PDI prepared in Comparative Example 1, and GO prepared in Comparative Example 2.

[0073] Figure 10 XPS comparison images of GO / SA-PDI (80%) prepared in Example 1, SA-PDI prepared in Comparative Example 1, and GO prepared in Comparative Example 2; where (a) is the full spectrum, (b) is the C 1s spectrum, and (c) is the N 1s spectrum.

[0074] Figure 11 The DRS comparison diagram shows the GO / SA-PDI (80%) prepared in Example 1, SA-PDI prepared in Comparative Example 1, and GO prepared in Comparative Example 2.

[0075] Figure 12 The graph shows a comparison of the photoelectric conversion performance of GO / SA-PDI (80%) prepared in Example 1 and SA-PDI prepared in Comparative Example 1; where (a) is the photocurrent response under alternating light and dark conditions; and (b) is the electrochemical impedance Nyquist plot under visible light and dark conditions.

[0076] Figure 13 This is a comparison chart of the degradation performance of sulfamethoxazole by the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7 after the addition of different active species capture agents.

[0077] Figure 14 ESR comparison chart of the photocatalytic water treatment method based on GO / SA-PDI (80%) prepared in Example 1, the photocatalytic water treatment method based on SA-PDI prepared in Comparative Example 1, and the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7. Detailed Implementation

[0078] The following embodiments further illustrate the content of the present invention, but should not be construed as limiting the present invention. Any modifications and substitutions made to the methods, steps, or conditions of the present invention without departing from the spirit and essence of the present invention are within the scope of the present invention.

[0079] Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

[0080] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0081] Example 1

[0082] A method for preparing a GO / SA-PDI photocatalyst includes the following steps:

[0083] (1) Weigh 1.373g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.495g of β-aminopropionic acid and 18g of imidazole and mix them. Under argon protection, heat and stir at 100℃ and 500r / min for 4h. After the product cools naturally to room temperature, add 100mL of anhydrous ethanol and 300mL of 2.0mol / L hydrochloric acid solution and stir at 500r / min for 15h. Centrifuge (8000r / min) to collect the precipitate, wash the precipitate with water until neutral, dry it under vacuum at 60℃ for 24h, and finally grind it by hand for 1h. The product obtained is carboxyl perylene imide.

[0084] (2) 100 mg of carboxylic acid perylene imide was dispersed in 36.2 mL of water and ultrasonically dispersed (560 W, 40 kHz) for 0.5 h. 151 μL of triethylamine was added and heated and stirred at 50 °C and 500 r / min for 2 h until the carboxylic acid perylene imide was completely dissolved. Then, 4.7 mL of 4.0 mol / L hydrochloric acid solution was added at 1 mL / min and heated and stirred at 50 °C and 500 r / min for 2 h until precipitation stopped. The self-assembled carboxylic acid perylene imide dispersion, namely SA-PDI dispersion, was prepared.

[0085] (3) Disperse graphite oxide powder in ultrapure water and sonicate it (560W, 40kHz) for 2h to prepare a 1mg / mL GO dispersion.

[0086] (4) Add 25 mL of GO dispersion prepared in step (3) to the SA-PDI dispersion prepared in step (2), sonicate (560 W, 40 kHz) for 2 h, heat and stir at 95 °C and 500 r / min for 4 h, centrifuge (8000 r / min) to collect the precipitate after the reaction is completed, wash the precipitate with water until neutral, vacuum dry at 60 °C for 24 h, and finally grind by hand for 1 h. The obtained product is recorded as GO / SA-PDI (80%) photocatalyst.

[0087] Example 2

[0088] Example 2 is basically the same as Example 1, except that the mass ratio of GO to SA-PDI is 1:19. The remaining steps and raw materials are the same as in Example 1. The resulting product is denoted as GO / SA-PDI (95%) photocatalyst.

[0089] Example 3

[0090] Example 3 is basically the same as Example 1, except that the mass ratio of GO to SA-PDI is 1:9. The remaining steps and raw materials are the same as in Example 1. The resulting product is denoted as GO / SA-PDI (90%) photocatalyst.

[0091] Example 4

[0092] Example 4 is basically the same as Example 1, except that the mass ratio of GO to SA-PDI is 3:7. The remaining steps and raw materials are the same as in Example 1. The resulting product is denoted as GO / SA-PDI (70%) photocatalyst.

[0093] Example 5

[0094] Example 5 is basically the same as Example 1, except that the mass ratio of GO to SA-PDI is 2:3. The remaining steps and raw materials are the same as in Example 1. The resulting products are denoted as GO / SA-PDI (60%) photocatalysts.

[0095] Example 6

[0096] Example 6 is basically the same as Example 1, except that the mass ratio of GO to SA-PDI is 1:1. The remaining steps and raw materials are the same as in Example 1. The resulting products are denoted as GO / SA-PDI (50%) photocatalysts.

[0097] Example 7

[0098] A photocatalytic self-Fenton water treatment method based on GO / SA-PDI includes the following steps:

[0099] (1) Weigh 1.373g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.495g of β-aminopropionic acid and 18g of imidazole and mix them. Under argon protection, heat and stir at 100℃ and 500r / min for 4h. After the product cools naturally to room temperature, add 100mL of anhydrous ethanol and 300mL of 2.0mol / L hydrochloric acid solution and stir at 500r / min for 15h. Centrifuge (8000r / min) to collect the precipitate, wash the precipitate with water until neutral, dry it under vacuum at 60℃ for 24h, and finally grind it by hand for 1h. The product obtained is carboxyl perylene imide.

[0100] (2) 100 mg of carboxylic acid perylene imide was dispersed in 36.2 mL of water and ultrasonically dispersed (560 W, 40 kHz) for 0.5 h. 151 μL of triethylamine was added and heated and stirred at 50 °C and 500 r / min for 2 h until the carboxylic acid perylene imide was completely dissolved. Then, 4.7 mL of 4.0 mol / L hydrochloric acid solution was added at 1 mL / min and heated and stirred at 50 °C and 500 r / min for 2 h until precipitation stopped. The self-assembled carboxylic acid perylene imide dispersion, namely SA-PDI dispersion, was prepared.

[0101] (3) Disperse graphite oxide powder in ultrapure water and sonicate it (560W, 40kHz) for 2h to prepare a 1mg / mL GO dispersion.

[0102] (4) Add 25 mL of GO dispersion prepared in step (3) to the SA-PDI dispersion prepared in step (2), sonicate (560 W, 40 kHz) for 2 h, heat and stir at 95 °C and 500 r / min for 4 h, centrifuge (8000 r / min) to collect the precipitate after the reaction is completed, wash the precipitate with water until neutral, vacuum dry at 60 °C for 24 h, and finally grind by hand for 1 h. The obtained product is recorded as GO / SA-PDI (80%) photocatalyst.

[0103] (5) Add 10 mg of GO / SA-PDI (80%) photocatalyst to the wastewater to be treated, disperse it by ultrasound (560W, 40kHz) for 0.5h, adjust the pH of the reaction system to 6 and the temperature to 25℃, stir at 500r / min for 2h to reach adsorption-desorption equilibrium, add 4 mg of ferric sulfate (the mass ratio of GO / SA-PDI (80%) photocatalyst to Fe salt is 5:2) to the reaction system, and then place the reaction system under an LED lamp for irradiation to initiate the photocatalytic self-Fenton reaction based on GO / SA-PDI (80%). During the reaction, oxygen is continuously introduced (1mL / min) to keep the solution in an oxygen saturated state.

[0104] Example 8

[0105] A photocatalytic self-Fenton water treatment method based on GO / SA-PDI includes the following steps:

[0106] (1) Weigh 1g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 0.1g of β-aminopropionic acid and 0.1g of imidazole and mix them. Under nitrogen protection, heat and stir at 80℃ and 50r / min for 0.1h. After the product cools naturally to room temperature, add 1mL of anhydrous methanol and 1mL of 0.01mol / L nitric acid solution and stir at 50r / min for 0.1h. Centrifuge (1000r / min) to collect the precipitate, wash the precipitate with water until neutral, freeze dry at 0℃ for 1h, and finally grind by hand for 0.1h. The product obtained is carboxyl perylene imide.

[0107] (2) Disperse 100 mg of carboxylic perylene imide in 5 mL of water and sonicate (200 W, 10 kHz) for 0.1 h. Add 5 μL of ethylenediamine and heat and stir at 30 °C and 50 r / min for 0.1 h until the carboxylic perylene imide is completely dissolved. Then add 0.5 mL of 0.01 mol / L nitric acid solution at 0.1 mL / min and heat and stir at 30 °C and 50 r / min for 0.1 h until precipitation stops. Prepare a self-assembled carboxylic perylene imide dispersion, namely SA-PDI dispersion.

[0108] (3) Disperse graphite oxide powder in ultrapure water and sonicate it (200W, 10kHz) for 0.1h to prepare a 0.01mg / mL GO dispersion;

[0109] (4) Add 10 mL of GO dispersion prepared in step (3) to the SA-PDI dispersion prepared in step (2), sonicate (200W, 10kHz) for 0.1 h, heat and stir at 30℃ and 50 r / min for 0.1 h, centrifuge (1000 r / min) to collect the precipitate after the reaction is completed, wash the precipitate with water until neutral, freeze dry at 0℃ for 1 h, and finally grind by hand for 0.1 h. The obtained product is called GO / SA-PDI (99.9%) photocatalyst.

[0110] (5) Add 10 mg of GO / SA-PDI (99.9%) photocatalyst to the wastewater to be treated, disperse it by ultrasound (200W, 10kHz) for 0.1h, adjust the pH of the reaction system to 1 and the temperature to 0℃, stir at 50r / min for 0.1h to reach adsorption-desorption equilibrium, add 0.05 mg of ferric nitrate to the reaction system (the mass ratio of GO / SA-PDI (99.9%) photocatalyst to Fe salt is 200:1), and then place the reaction system under a xenon lamp for irradiation to initiate the photocatalytic self-Fenton reaction based on GO / SA-PDI (99.9%). During the reaction, continuously introduce air (0.1mL / min) to keep the solution in an oxygen-saturated state.

[0111] Example 9

[0112] A photocatalytic self-Fenton water treatment method based on GO / SA-PDI includes the following steps:

[0113] (1) Weigh 1g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 10g of β-aminopropionic acid and 50g of imidazole and mix them. Under helium protection, heat and stir the mixture at 150℃ and 1500r / min for 30h. After the product cools naturally to room temperature, add 200mL of anhydrous isopropanol and 1000mL of 18mol / L sulfuric acid solution. Stir at 1500r / min for 30h. Centrifuge (15000r / min) to collect the precipitate. Wash the precipitate with water until neutral. Dry it at 100℃ and normal pressure for 50h. Finally, grind it manually for 10h. The product obtained is carboxyl perylene imide.

[0114] (2) 100 mg of carboxylic perylene imide was dispersed in 2000 mL of water and ultrasonically dispersed (800 W, 50 kHz) for 10 h. 2000 μL of ethylenediamine was added and heated and stirred at 100 °C and 1500 r / min for 10 h until the carboxylic perylene imide was completely dissolved. Then, 200 mL of 18 mol / L sulfuric acid solution was added at 100 mL / min and heated and stirred at 100 °C and 1500 r / min for 10 h until precipitation stopped. The self-assembled carboxylic perylene imide dispersion, namely SA-PDI dispersion, was prepared.

[0115] (3) Disperse graphene oxide powder in ultrapure water and sonicate it (800W, 50kHz) for 10h to prepare a GO dispersion of 100mg / mL.

[0116] (4) Add 10 mL of GO dispersion prepared in step (3) to the SA-PDI dispersion prepared in step (2), sonicate (800 W, 50 kHz) for 10 h, heat and stir at 100 °C and 1500 r / min for 10 h, centrifuge (15000 r / min) to collect the precipitate after the reaction is completed, wash the precipitate with water until neutral, dry at 100 °C and normal pressure for 50 h, and finally grind by hand for 10 h. The obtained product is recorded as GO / SA-PDI (9.1%) photocatalyst.

[0117] (5) Add 10 mg of GO / SA-PDI (9.1%) photocatalyst to the wastewater to be treated, disperse it by ultrasound (800W, 50kHz) for 10 h, adjust the pH of the reaction system to 14 and the temperature to 100℃, stir at 1500 r / min for 10 h to reach adsorption-desorption equilibrium, add 200 mg of ferric chloride (the mass ratio of GO / SA-PDI (9.1%) photocatalyst to Fe salt is 1:20) to the reaction system, and then place the reaction system under a high-pressure mercury lamp for irradiation to initiate the photocatalytic self-Fenton reaction based on GO / SA-PDI (9.1%). During the reaction, continuously introduce oxygen-argon mixed gas (10 mL / min) to keep the solution in an oxygen-saturated state.

[0118] Comparative Example 1

[0119] The preparation of SA-PDI photocatalysts via supramolecular self-assembly includes the following steps:

[0120] (1) Weigh 1.373g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.495g of β-aminopropionic acid and 18g of imidazole and mix them. Under argon protection, heat and stir at 100℃ and 500r / min for 4h. After the product cools naturally to room temperature, add 100mL of anhydrous ethanol and 300mL of 2.0mol / L hydrochloric acid solution and stir at 500r / min for 15h. Centrifuge (8000r / min) to collect the precipitate, wash the precipitate with water until neutral, dry it under vacuum at 60℃ for 24h, and finally grind it by hand for 1h. The product obtained is carboxyl perylene imide.

[0121] (2) 100 mg of carboxylic acid perylene imide was dispersed in 36.2 mL of water and ultrasonically dispersed (560 W, 40 kHz) for 0.5 h. 151 μL of triethylamine was added and heated and stirred at 50 °C and 500 r / min for 2 h until the carboxylic acid perylene imide was completely dissolved. Then, 4.7 mL of 4.0 mol / L hydrochloric acid solution was added at 1 mL / min and heated and stirred at 50 °C and 500 r / min for 2 h until precipitation stopped. After the reaction was completed, the precipitate was collected by centrifugation (8000 r / min), washed with water until neutral, dried under vacuum at 60 °C for 24 h, and finally manually ground for 1 h. The product obtained is the SA-PDI photocatalyst.

[0122] Comparative Example 2

[0123] The preparation of GO by ultrasonication includes the following steps:

[0124] 100 mg of graphite oxide powder was dispersed in water and ultrasonically treated (560 W, 40 kHz) for 2 h to prepare a 1 mg / mL GO dispersion. The dispersion was then vacuum dried at 60 °C for 24 h to obtain the GO product.

[0125] Comparative Example 3

[0126] The preparation of g-C3N4 photocatalysts via high-temperature polycondensation includes the following steps:

[0127] Weigh 10g of melamine and transfer it to a 50mL covered crucible. Heat the crucible to 550℃ in a muffle furnace at a heating rate of 2℃ / min. Calcinate the product at 550℃ for 4 hours. After the calcined product cools naturally, grind it by hand for 1 hour. The resulting product is g-C3N4 photocatalyst.

[0128] Comparative Example 4

[0129] The preparation of GO / SA-PDI (80%) by physical mixing includes the following steps:

[0130] 80 mg SA-PDI and 20 mg GO were manually ground and mixed for 1 hour. The resulting product was denoted as GO / SA-PDI (80%) (physical mixture).

[0131] Comparative Example 5

[0132] The in-situ preparation of carboxyl perylene imide / oxygen-doped carbon nitride nanosheet composite photocatalysts includes the following steps:

[0133] (1) 3-Amino-1,2,4-triazole was placed in a crucible and placed in a muffle furnace. The temperature was increased to 550℃ at a rate of 2℃ / min and calcined for 4h. The product was ground to obtain brick-red blocky carbon nitride. The blocky carbon nitride was ground, placed in a crucible, placed in a muffle furnace, and calcined again at a rate of 5℃ / min to 500℃ for 2h. The product was ground to obtain carbon nitride nanosheets. 0.9g of carbon nitride nanosheets were dispersed in 100mL of 30vol%H2O2 aqueous solution and sonicated (560W, 40kHz) for 0.5h. The dispersion was then transferred to a hydrothermal reactor and heated at 120℃ for 6h. The precipitate was collected by centrifugation, washed several times with water, dried, and then manually ground for 1h. The obtained product was oxygen-doped carbon nitride nanosheets (O-CN).

[0134] (2) Mix 1.373 g of 3,4,9,10-tetracarboxylic acid dianhydride, 18 g of imidazole and 2.495 g of β-aminopropionic acid, and stir at 100 °C for 4 h under an argon atmosphere. After the product is naturally cooled to room temperature, add 100 mL of ethanol and 300 mL of 2.0 mol / L hydrochloric acid, and stir for 15 h. Filter the mixture with a 0.45 μm aqueous filter membrane to collect the precipitate, wash the precipitate several times with water until neutral, dry it and grind it into powder. The product obtained is carboxyl perylene imide. Disperse 330 mg of carboxyl perylene imide in 123 mL of water by ultrasonication, add 515 μL of triethylamine and stir for 2 h to completely dissolve the carboxyl perylene imide and form a carboxyl perylene imide solution.

[0135] (3) Weigh 100 mg of O-CN, disperse it in 30 mL of water, and sonicate it (560 W, 40 kHz) for 2 h. Add a certain volume of PDI solution, in which the mass fraction of PDI relative to O-CN is 40%. Stir for 1 h, sonicate (560 W, 40 kHz) for 15 min, and then add a certain volume of 4 mol / L nitric acid (containing carboxyperylimide and nitric acid in a mass-volume ratio of 1 mg: 0.0511 mL). Heat and stir in a water bath at 60 °C for 1.5 h, centrifuge to collect the precipitate, wash the precipitate several times with water, dry it, and grind it manually for 1 h. The product obtained is the self-assembled carboxyperylimide / oxygen-doped carbon nitride nanosheet (SA-PDI / O-CN) composite photocatalyst.

[0136] Comparative Example 6

[0137] The in-situ preparation of cobalt-intercalated nitrogen-rich porous carbon material / self-assembled carboxyl-containing perylene imide composite photocatalysts includes the following steps:

[0138] (1) 2 mmol Co(NO3)2·6H2O and 12 mmol 2-methylimidazole were dissolved in 30 mL and 10 mL of methanol, respectively, to form Co(NO3)2·6H2O solution and 2-methylimidazole solution, respectively. The 2-methylimidazole solution was then slowly added to the Co(NO3)2·6H2O solution. The mixture was stirred at 25 °C and 500 r / min for 5 h, and allowed to stand for 24 h. The precipitate was collected by centrifugation at 8000 r / min. The precipitate was washed several times with ethanol and dried at 60 °C for 12 h. The dried product was manually ground for 1 h. The resulting powder product was the cobalt-based metal-organic framework material (Co-MOF). Next, the Co-MOF was placed in a quartz boat and heated to 600 °C at a heating rate of 1 °C / min in a tube furnace under a nitrogen atmosphere. The mixture was then calcined at a constant temperature for 2 h. After cooling, the product was ground for 1 h. The resulting product was the cobalt-embedded nitrogen-rich porous carbon material (Co-NC).

[0139] (2) Weigh 1.373g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.495g of β-aminopropionic acid and 18g of imidazole. Under argon protection, heat the mixture to 140℃ and stir under reflux at 500r / min for 4h. After the product cools naturally to room temperature, add 100mL of anhydrous ethanol and 300mL of 2.0mol / L hydrochloric acid. Stir at 500r / min for 15h. Centrifuge at 8000r / min to separate the precipitate. Wash the precipitate with water until neutral and dry at 60℃ for 20h. Grind the product for 1h. The obtained product is carboxyl perylene imide. Weigh 534 mg of carboxylic acid perylene imide into 200 mL of water and sonicate (560 W, 40 kHz) for 40 min. Add 834 μL of triethylamine and stir at 500 r / min for 2 h to completely dissolve the carboxylic acid perylene imide to form a carboxylic acid perylene imide solution. Then add 27.3 mL of 4.0 mol / L hydrochloric acid and stir at 500 r / min for 1 h to obtain a self-assembled carboxylic acid perylene imide dispersion, SA-PDI dispersion.

[0140] (3) Weigh 200 mg of Co-NC powder and sonicate it in 20 mL of water (560 W, 40 kHz) for 40 min to obtain a 10 mg / mL Co-NC dispersion. Then add it to the SA-PDI dispersion so that the mass fraction of SA-PDI relative to Co-NC / SA-PDI is 70%. Stir the mixture at 60 °C and 500 r / min for 1 h, then sonicate it (560 W, 40 kHz) for 1 h. After the mixture cools, centrifuge it at 8000 r / min to collect the precipitate. Wash the precipitate with water until neutral, and vacuum dry it at 60 °C for 20 h. Grind the product by hand for 1 h. The product obtained is the cobalt embedded nitrogen-rich porous carbon material / self-assembled carboxyl perylene imide (Co-NC / SA-PDI) composite photocatalyst.

[0141] Comparative Example 7

[0142] A photocatalytic self-Fenton water treatment method based on SA-PDI includes the following steps:

[0143] (1) Weigh 1.373g of 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2.495g of β-aminopropionic acid and 18g of imidazole and mix them. Under argon protection, heat and stir at 100℃ and 500r / min for 4h. After the product cools naturally to room temperature, add 100mL of anhydrous ethanol and 300mL of 2.0mol / L hydrochloric acid solution and stir at 500r / min for 15h. Centrifuge (8000r / min) to collect the precipitate, wash the precipitate with water until neutral, dry it under vacuum at 60℃ for 24h, and finally grind it by hand for 1h. The product obtained is carboxyl perylene imide.

[0144] (2) 100 mg of carboxylic acid perylene imide was dispersed in 36.2 mL of water and ultrasonically dispersed (560 W, 40 kHz) for 30 min. 151 μL of triethylamine was added and heated and stirred at 50 °C and 500 r / min for 2 h until the carboxylic acid perylene imide was completely dissolved. Then, 4.7 mL of 4.0 mol / L hydrochloric acid solution was added at 1 mL / min and heated and stirred at 50 °C and 500 r / min for 2 h until precipitation stopped. After the reaction was completed, the precipitate was collected by centrifugation (8000 r / min), washed with water until neutral, dried under vacuum at 60 °C for 24 h, and finally manually ground for 1 h. The product obtained is the SA-PDI photocatalyst.

[0145] (3) Add 10 mg of SA-PDI photocatalyst to the wastewater to be treated, disperse it by ultrasound (560 W, 40 kHz) for 0.5 h, adjust the pH of the reaction system to 6 and the temperature to 25 °C, stir at 500 r / min for 2 h to reach adsorption-desorption equilibrium, add 4 mg of ferric sulfate (the mass ratio of SA-PDI photocatalyst to Fe salt is 5:2) to the reaction system, and then place the reaction system under an LED lamp for irradiation to initiate the SA-PDI-based photocatalytic self-Fenton reaction. During the reaction, oxygen is continuously introduced (1 mL / min) to keep the solution in an oxygen-saturated state.

[0146] Comparative Example 8

[0147] The Fenton water treatment method includes the following steps:

[0148] Add 4 mg of ferrous salt to the wastewater to be treated and stir at 500 r / min for 0.5 h. Add H2O2 to the reaction system to make its concentration 38.3 μmol / L to initiate the Fenton reaction.

[0149] Example 10: Performance Test of H2O2 Synthesis

[0150] The synthesis of H2O2 was carried out using a PCX50C multichannel reactor from Profilo. Visible light was emitted from a 10W LED lamp (100mW / cm²). 2The following steps were taken: First, 25 mg of photocatalyst was added to 50 mL of SDM solution (10 ppm), and ultrasonically dispersed for 0.5 h. The pH of the reaction system was adjusted to 7 and the temperature to 25 °C. The mixture was stirred continuously in the dark for 2 h. After turning on the light, 1 mL of the reaction solution was sampled at regular intervals, 3 mL of ultrapure water was added, and the reaction solution was centrifuged (11000 r / min) to remove the photocatalyst. The supernatant was filtered through a 0.22 μm Millipore filter. During the reaction, oxygen was continuously introduced (1 mL / min) to keep the solution oxygen-saturated. The content of H2O2 synthesized by photocatalytic method was analyzed: 1 mL of potassium hydrogen phthalate aqueous solution (0.1 mol / L) and 1 mL of potassium iodide aqueous solution (0.4 mol / L) were added to 3 mL of supernatant, and the mixture was shaken on a shaker for 1 h. Then, the absorbance of the reaction solution at 350 nm was measured by a UV-Vis spectrophotometer (Shimadzu UV-3600Plus). The concentration of H2O2 produced at different reaction stages was calculated according to the H2O2 concentration-absorbance standard curve.

[0151] Figure 1 The table shows a comparison of the H2O2 synthesis performance of GO / SA-PDI prepared in Examples 1-6 with SA-PDI prepared in Comparative Example 1, g-C3N4 prepared in Comparative Example 3, GO / SA-PDI (80%) (physical mixing) prepared in Comparative Example 4, carboxyl perylene imide / oxygen-doped carbon nitride nanosheets (SA-PDI / O-CN) prepared in Comparative Example 5, and cobalt-intercalated nitrogen-rich porous carbon material / self-assembled carboxyl perylene imide (Co-NC / SA-PDI) prepared in Comparative Example 6. Figure 1It was found that the SA-PDI, g-C3N4, GO / SA-PDI (80%) (physical mixture), SA-PDI / O-CN, and Co-NC / SA-PDI samples exhibited low photocatalytic activity for H2O2 synthesis, with H2O2 yields of approximately 18.3 μmol / L, 2.5 μmol / L, 16.7 μmol / L, 25.6 μmol / L, and 36.8 μmol / L, respectively, within 2 h. In contrast, all composite ratios of GO / SA-PDI photocatalysts showed higher H2O2 synthesis performance, and the photocatalytic activity of GO / SA-PDI for H2O2 synthesis initially increased and then decreased with increasing GO mass ratio. Among them, GO / SA-PDI (80%) showed the best performance in synthesizing H2O2, with an H2O2 yield of 74.8 μmol / L within 2 hours. This is 4.1 times that of SA-PDI (18.3 μmol / L), 29.9 times that of g-C3N4 (2.5 μmol / L), 4.5 times that of GO / SA-PDI (80%) (physical mixture) (16.7 μmol / L), 2.9 times that of SA-PDI / O-CN (25.6 μmol / L), and 2.0 times that of Co-NC / SA-PDI (36.8 μmol / L). The improved performance of GO / SA-PDI photocatalytic synthesis of H2O2 is due to two main factors. First, the introduction of GO enhances the light absorption capacity of the composite material, promoting the generation of more photogenerated charges and exposing more reactive sites, thereby strengthening the composite material's adsorption capacity for O2 and facilitating the participation of photogenerated charges in the reduction of O2 to synthesize H2O2. Second, GO and SA-PDI are tightly bound through π-π interactions, triggering an electron delocalization effect and promoting interlayer electron transfer. Simultaneously, the conductive carbon matrix of GO helps accelerate the migration of photogenerated charges at the interface, further improving the performance of photocatalytic H2O2 synthesis. However, since GO / SA-PDI (80%) (physical mixture) is prepared by manual grinding, there is no tight interaction between GO and SA-PDI. GO cannot effectively enhance the light absorption capacity of the composite material, increase the number of surface active sites, or accelerate the separation and migration rate of photogenerated charges. Therefore, the photocatalytic activity of GO / SA-PDI (80%) (physical mixture) is significantly lower than that of GO / SA-PDI (80%). Compared to SA-PDI / O-CN and Co-NC / SA-PDI composite photocatalysts, GO / SA-PDI exhibits more significant photocatalytic performance in synthesizing H2O2, indicating that the modification strategy of combining with GO is more conducive to improving the photocatalytic activity of SA-PDI.In the composite material, when the GO content is too low, the dispersion of SA-PDI particles on the GO nanosheet surface is not uniform enough, and the number of GO particles acting as electron acceptors is limited, resulting in insufficient surface active sites and low migration rate of photogenerated charges, thus leading to a minimal improvement in the catalytic activity of the composite material. Conversely, when the GO content is too high, the proportion of SA-PDI decreases, resulting in fewer photogenerated carriers and longer migration distances of photogenerated electrons, thereby affecting the improvement in the catalytic activity of the composite material. These results indicate that combining SA-PDI and GO can indeed improve the photocatalytic activity of the composite material, and the improvement in photocatalyst performance is a result of the synergistic effect of SA-PDI and GO. This demonstrates that compared to the SA-PDI photocatalyst, GO / SA-PDI exhibits superior photocatalytic synthesis performance for H2O2.

[0152] Example 11 Antibiotic Degradation Performance Test

[0153] Sulfamethoxazole (SMX) was selected as the target degradation product. The degradation of SMX (50 mL, 10 ppm) was conducted using a Polyfibrillated PCX50C multichannel reactor. Visible light was emitted from a 10W LED lamp (100 mW / cm²). 2 Provided, the reaction system was adjusted to pH=7 and temperature=25℃. In the photocatalytic reaction system, the photocatalyst concentration was 0.2 g / L; in the photocatalytic self-Fenton reaction system, the photocatalyst concentration was 0.2 g / L, Fe... 3+ The salt concentration is 0.08 g / L; in the Fenton reaction system, Fe... 2+ The salt concentration was 0.08 g / L, and the H₂O₂ concentration was 38.3 μmol / L. After the degradation reaction started, 2 mL of the reaction solution was taken at regular intervals, centrifuged (10000 r / min) to remove the photocatalyst, and the supernatant was filtered through a 0.22 μm Millipore filter. The concentration of SMX in the supernatant was detected at 270 nm using high-performance liquid chromatography (Waters 1525) at a flow rate of 1 mL / min (Waters-C18, acetonitrile to 0.1% acetic acid aqueous solution volume ratio of 40:60). The TOC content in the supernatant was detected using a total organic carbon analyzer (Shimadzu, TOC-V CPH).

[0154] Figure 2 This is a comparison of the SMX degradation performance under different conditions using the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) prepared in Example 1. Figure 2 (a) It can be seen that the addition of Fe 3+ The salt reaction system showed the best degradation effect on SDM, GO / SA-PDI (80%) + Fe 3+Within 10 minutes of light irradiation, the degradation rate of SDM reached 82.3%, which is significantly higher than that of GO / SA-PDI (80%) + Fe. 2+ This may be attributed to Fe 3+ Reduced to Fe 2+ The addition of Fe consumes a large number of photogenerated electrons, inhibiting electron-hole recombination and thus facilitating the release of more holes to participate in the oxidation reaction. This increases the degradation performance of the reaction system for organic matter. Therefore, the addition of Fe is chosen. 3+ Salt was used in subsequent experiments. Figure 2 (b) It can be seen that when Fe 3+ Increasing the salt addition from 2 mg to 4 mg significantly improved the degradation activity, and this effect was further enhanced with increasing Fe content. 3+ The degradation activity gradually increased with increasing salt content, reaching its peak at an iron salt content of 8 mg. This was due to excessive Fe... 3+ The addition of salt will also increase the cost of water treatment, taking into account Fe. 3+ The recommended salt dosage is 4 mg. Figure 2 (c) It can be seen that the reaction system at pH=4 has the best SMX degradation effect. After 10 min of light irradiation, the SMX degradation rate reaches 83.1%, which is slightly higher than the degradation rates at pH=5.5 and pH=7.0. However, the degradation effect does not change significantly with pH. In the case of the Fenton system, in order to prevent Fe from the system... 2+ / Fe 3+ Ions precipitate, and the Fenton reaction requires weakly acidic conditions. However, the photocatalytic self-Fenton system overcomes the limitation of the Fenton reaction being greatly affected by pH, and can carry out the reaction in a wider pH range. Taking all factors into consideration, we chose to conduct subsequent experiments under initial neutral conditions, without adding acid to adjust the pH value of the photocatalytic self-Fenton reaction system, thus demonstrating the great potential of the photocatalytic self-Fenton water treatment method in water purification.

[0155] Figure 3 This is a comparison chart showing the degradation rates of sulfamethoxazole and its total organic carbon (TOC) removal rates based on the photocatalytic water treatment method using GO / SA-PDI (80%) prepared in Example 1, the photocatalytic water treatment method using SA-PDI prepared in Comparative Example 1, the photocatalytic self-Fenton water treatment method using GO / SA-PDI (80%) in Example 7 (GO / SA-PDI(80%)-PSF), the photocatalytic self-Fenton water treatment method using SA-PDI in Comparative Example 7 (SA-PDI-PSF), and the Fenton water treatment method in Comparative Example 8. Figure 3 As shown in (a) and 3(b), the GO / SA-PDI (80%) photocatalytic system degrades approximately 31.7% of SMX within 1 hour, and the apparent rate constant (k) obtained by fitting the pseudo-first-order kinetic equation is 0.0042 min.-1 It is the SA-PDI photocatalytic system (0.0021 min). -1 The efficiency of photocatalytic degradation is 2.0 times that of GO, indicating that the introduction of GO can improve the separation and migration rate of photogenerated charges in the composite material, while exposing more active sites, thus further improving the photocatalytic degradation efficiency. This can be achieved by adding Fe. 3+ Both photocatalysts exhibited superior degradation activity, indicating that the photocatalytic self-Fenton system can further enhance the oxidation capacity of the reaction system. The GO / SA-PDI (80%)-based photocatalytic self-Fenton system degraded approximately 93.0% of SMX within 1 hour, with a k-value as high as 0.18 min. -1 The results were 42.8 times that of the GO / SA-PDI (80%) photocatalytic system and 0.069 min that of the SA-PDI photocatalytic self-Fenton system. -1 The yield of GO / SA-PDI (80%) in the SMX degradation reaction system was 2.6 times that of the SA-PDI-based photocatalytic system, and 85.7 times that of the SA-PDI-based system. Since the cumulative yield of H2O2 synthesized after 1 hour of reaction in the SMX degradation system was 38.3 μmol / L, the amount of H2O2 added in the homogeneous Fenton reaction used for comparison was set at 38.3 μmol / L. The k-value of the photocatalytic degradation of SMX from the Fenton system based on GO / SA-PDI (80%) was approximately 0.0026 min. -1 69.2 times that of ) . TOC can be used to analyze and evaluate the ability of water treatment technologies to remove antibiotics through mineralization. Figure 3 (c) It can be seen that the photocatalytic system based on GO / SA-PDI (80%) achieved a TOC removal rate of 18.2% for SMX within 1 hour, which is 2.4 times that of the SA-PDI photocatalytic system (7.5%), indicating that the introduction of GO improved the mineralization ability of the composite photocatalytic material. The addition of Fe... 3+ Subsequently, the TOC removal rates of both photocatalysts were significantly improved, indicating that the photocatalytic self-Fenton system can further enhance the mineralization capacity of the reaction system. The GO / SA-PDI (80%)-based photocatalytic self-Fenton system achieved a TOC removal rate of 51.4% for SMX within 1 hour, which is 2.8 times that of the GO / SA-PDI (80%)-based photocatalytic system (18.2%), 1.6 times that of the SA-PDI-based photocatalytic self-Fenton system (31.7%), 6.9 times that of the SA-PDI-based photocatalytic system (7.5%), and 7.7 times that of the Fenton system (6.7%). This is mainly because, compared to photocatalytic water treatment methods, the GO / SA-PDI (80%)-based photocatalytic self-Fenton water treatment method generates more ·OH and photogenerated holes, further enhancing its oxidation capacity and mineralization efficiency; compared to the Fenton water treatment method, the GO / SA-PDI (80%)-based photocatalytic self-Fenton water treatment method also shows a higher Fe content.3+ It can be promptly reduced to Fe by photogenerated electrons. 2+ Promote Fe 3+ / Fe 2+ The cyclic transformation significantly increases the in-situ production of H2O2 and Fe from GO / SA-PDI (80%). 2+ The efficiency of generating ·OH through the self-Fenton reaction further enhances the oxidation capacity of the reaction system. This demonstrates that the GO / SA-PDI (80%) photocatalyst exhibits superior organic matter degradation performance and mineralization efficiency compared to the SA-PDI photocatalyst. Furthermore, it demonstrates that the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) demonstrates superior organic matter degradation performance and mineralization efficiency compared to photocatalysis alone and Fenton water treatment methods.

[0156] Figure 4 This is a cyclic degradation activity diagram of the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7. Figure 4 It can be seen that after four consecutive cycles of degradation, the activity of the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) for degrading SMX did not decrease significantly, indicating that it has good stability.

[0157] Example 12 Test of performance in killing drug-resistant bacteria

[0158] Sulfonamide ARBs were selected as the target bacterial strain, and antibacterial experiments were conducted using a Polyfibrillated PCX50C multichannel reactor. Visible light was provided by a 10W LED lamp (100mW / cm²). 2 Provided, the reaction system was adjusted to pH=7 and temperature=25℃. In the photocatalytic reaction system, the photocatalyst concentration was 0.2 g / L; in the photocatalytic self-Fenton reaction system, the photocatalyst concentration was 0.2 g / L, Fe... 3+ The salt concentration is 0.08 g / L; in the Fenton reaction system, Fe... 2+ The salt concentration was 0.08 g / L, and the H2O2 concentration was 38.3 μmol / L. Sulfonamide ARBs were incubated in Luria Bertani (LB) liquid medium at 37°C with shaking for 4 h. Bacterial cells were collected by centrifugation (4000 r / min, 5 min), washed several times with sterile physiological saline, and then resuspended in physiological saline solution. The concentration of sulfonamide ARBs in the antibacterial experiment was approximately 1 × 10⁻⁶ g / L. 7 cfu / mL. After the antibacterial reaction begins, equal amounts of bacterial suspension are taken at regular time intervals, diluted with sterile physiological saline, and 0.1 mL of the diluted solution is spread on LB solid medium and incubated at 37°C for 12 h. The number of bacteria in the bacterial suspension is counted using the plate count method. Each experiment is performed in triplicate. The experimental apparatus and physiological saline solution are sterilized at 121°C for 20 min.

[0159] Figure 5 This is a comparison chart showing the performance of the photocatalytic water treatment method based on GO / SA-PDI (80%) prepared in Example 1, the photocatalytic water treatment method based on SA-PDI prepared in Comparative Example 1, the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7 (GO / SA-PDI(80%)-PSF), the photocatalytic self-Fenton water treatment method based on SA-PDI in Comparative Example 7 (SA-PDI-PSF), and the Fenton water treatment method in Comparative Example 8 in killing sulfonamide ARBs. Figure 5 It can be seen that both the light-controlled group (without photocatalyst but with visible light irradiation) and the dark-controlled group (with photocatalyst but without visible light irradiation) showed poor removal effects on sulfonamide ARBs. The GO / SA-PDI (80%) photocatalytic system achieved a removal rate of 54.7% for sulfonamide ARBs within 15 minutes, while the SA-PDI-based system only achieved 14.8%. This is attributed to the fact that the introduction of GO enhances the material's light absorption capacity, promotes photogenerated charge transfer, and exposes more reactive sites, thereby improving the photocatalytic antibacterial performance of the GO / SA-PDI (80%) composite material. Furthermore, it can be seen that the SA-PDI-based and GO / SA-PDI (80%) photocatalytic self-Fenton systems showed significantly better sterilization effects on sulfonamide ARBs than the photocatalytic system, both effectively killing almost all drug-resistant bacteria within 15 minutes. However, comparison reveals that the GO / SA-PDI (80%) photocatalytic self-Fenton system achieved a 92.9% removal rate of sulfonamide ARBs within 10 minutes, while the SA-PDI-based system only achieved 72.6%. This indicates that the synergistic effect of introducing GO and the photocatalytic self-Fenton system is crucial for improving the removal performance of drug-resistant bacteria. Furthermore, the Fenton system only achieved a 16.3% removal rate of sulfonamide ARBs within 15 minutes, significantly lower than the GO / SA-PDI (80%) system. This demonstrates that the GO / SA-PDI (80%) photocatalyst exhibits superior antibacterial performance compared to the SA-PDI photocatalyst. Simultaneously, this demonstrates that the GO / SA-PDI (80%) photocatalytic self-Fenton water treatment method possesses superior antibacterial performance compared to both photocatalysis and Fenton water treatment methods alone.

[0160] Example 13 Performance test for removing resistance genes

[0161] Using sulfonamide ARGs(sul1) as the target resistance gene, 200 mL of environmental water sample containing sulfonamide ARGs(sul1) was treated. The experiment was conducted using a Polyfiber PCX50C multichannel reactor, with visible light provided by a 10W LED lamp (100mW / cm²). 2 Provided, the reaction system was adjusted to pH=7 and temperature=25℃. In the photocatalytic reaction system, the photocatalyst concentration was 0.25 g / L; in the photocatalytic self-Fenton reaction system, the photocatalyst concentration was 0.25 g / L, Fe... 3+ The salt concentration is 0.1 g / L; in the Fenton reaction system, Fe... 2+ The salt concentration was 0.1 g / L, and the H2O2 concentration was 38.3 μmol / L. The reaction to remove resistance genes was carried out under stirring conditions for 2 h. After the reaction, the water sample was filtered, and the filter membrane was cut into pieces. DNA was extracted using a soil genomic DNA extraction kit. The concentration of DNA in the sample was detected using a Nanodrop micro spectrophotometer. The absolute abundance of sulfonamide ARGs (sul1) in the sample was detected using a real-time quantitative PCR (qPCR) analyzer (StepOnePlus, ABI). Each experiment was performed in triplicate.

[0162] Figure 6 This is a comparison chart showing the performance of the photocatalytic water treatment method based on GO / SA-PDI (80%) prepared in Example 1, the photocatalytic water treatment method based on SA-PDI prepared in Comparative Example 1, the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7, the photocatalytic self-Fenton water treatment method based on SA-PDI in Comparative Example 7, and the Fenton water treatment method in Comparative Example 8 in removing sulfonamide ARGs. Figure 6It was found that after 2 hours of reaction, the removal rate of sulfonamide ARGs (sul1) in the water sample by the GO / SA-PDI (80%) photocatalytic system reached 66.0%, which is 2.4 times that of the SA-PDI photocatalytic system (27.4%). This is attributed to the fact that the introduction of GO enhances the light absorption capacity of the material, promotes the migration of photogenerated charges, and exposes more active sites, thereby improving the performance of GO / SA-PDI (80%) in removing ARGs. Compared with the photocatalytic system, the removal efficiency of sulfonamide ARGs (sul1) by the SA-PDI and GO / SA-PDI (80%) photocatalytic self-Fenton system is significantly improved. Under the same conditions, the GO / SA-PDI (80%) photocatalytic self-Fenton system achieved the best removal rate of sulfonamide ARGs (sulfuric acid precipitates) in the water sample, reaching 99.9%. This is 3.6 times the removal rate of the SA-PDI-based photocatalytic system (27.4%), 1.3 times that of the SA-PDI-based photocatalytic self-Fenton system (75.1%), 1.5 times that of the GO / SA-PDI-based photocatalytic system (66.0%), and 3.9 times that of the Fenton system (25.6%). In summary, the synergistic effect of introducing GO and the photocatalytic self-Fenton system can further enhance the oxidation capacity of the SA-PDI reaction system, thereby improving the performance of ARG removal. This demonstrates that the GO / SA-PDI (80%) photocatalyst has superior performance in removing ARGs compared to the SA-PDI photocatalyst. Meanwhile, it was demonstrated that the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) has superior performance in removing sulfonamide ARGs compared to photocatalysis alone and Fenton water treatment methods.

[0163] Transmission electron microscope (TEM) images were captured using a transmission electron microscope (JEOL JEM-2100) with an electron beam acceleration voltage of 200 kV. Figure 7 TEM comparison images of GO / SA-PDI (80%) prepared in Example 1, SA-PDI prepared in Comparative Example 1, and GO prepared in Comparative Example 2. Figure 7 (a) shows that GO exhibits a two-dimensional nanosheet morphology. From Figure 7 (b) It can be seen that SA-PDI is in the form of nanofibers, with a diameter of approximately 20-40 nm and a length of approximately 100-400 nm. Figure 7 (c) It can be seen that after SA-PDI is combined with GO, SA-PDI particles are uniformly dispersed on GO nanosheets. This heterogeneous structure of GO / SA-PDI (80%) is beneficial to increasing the reactive sites.

[0164] The X-ray diffraction spectra (XRD) of the samples were studied using a Bruker D2-phaser X-ray diffractometer (CuKα, 30kV, 10mA). Figure 8The images show XRD patterns comparing the GO / SA-PDI prepared in Examples 1-6 with the SA-PDI prepared in Comparative Example 1 and the GO prepared in Comparative Example 2. Figure 8 It is observed that GO exhibits a sharp diffraction peak near 11°, while in the GO / SA-PDI composite, this peak shifts to around 12° and becomes a broad diffraction peak, indicating that GO forms a loosely stacked network structure within the composite. As the mass percentage of GO in the composite increases, the characteristic diffraction peak of GO / SA-PDI at 12° also gradually strengthens, indicating successful bonding between GO and SA-PDI. SA-PDI has high crystallinity and exhibits multiple characteristic diffraction peaks in the range of 5°–28°, with the characteristic peak at 26.2° corresponding to a π-π stacking structure. Compared to SA-PDI, the diffraction peak corresponding to the π-π stacking structure in the GO / SA-PDI composite shifts slightly to lower angles, primarily attributed to the π-π interaction between SA-PDI and GO.

[0165] The Raman spectra of the samples were measured using a microconfocal Raman spectrometer (Thermofisher DXR2xi) with an excitation wavelength of 532 nm. Figure 9 Raman comparison images of GO / SA-PDI (80%) prepared in Example 1, SA-PDI prepared in Comparative Example 1, and GO prepared in Comparative Example 2. Figure 9 It can be seen that GO exists at 1346cm. -1 and 1590cm -1 The two peaks at this point correspond to the disorder vibration peak (D band) and the graphite peak (G band), respectively. SA-PDI is located at 1586 cm⁻¹. -1 The vibrational peak at 1298 cm⁻¹ is attributed to the stretching vibrations of C=C / CC and C=O in the benzene ring. These two structural vibrational peaks are highly sensitive to π-π packing. -1 The vibration peak at this location corresponds to the CH vibration during planar bending, and this peak does not show significant variation with π-π packing structures. A value of 1586 cm⁻¹ is typically used. -1 and 1298cm -1 The ratio of peak intensities at each peak reflects the degree of π-π packing of SA-PDI. Calculations show that the strength ratio of SA-PDI is 0.74, while that of GO / SA-PDI (80%) is 0.86. The significant increase in the strength ratio of the composite material indicates that the introduction of GO promotes the π-π packing of SA-PDI, enhances the electron delocalization effect, and thus increases the interlayer electron transfer rate. Furthermore, compared to SA-PDI, the peak position of GO / SA-PDI (80%) shifts towards higher wavenumbers, further indicating a π-π interaction between GO and SA-PDI.

[0166] The X-ray photoelectron spectroscopy (XPS) of the samples was measured using an EscaLab 250Xi spectrometer. Figure 10 XPS comparison graphs of GO / SA-PDI (80%) prepared in Example 1, SA-PDI prepared in Comparative Example 1, and GO prepared in Comparative Example 2. Figure 10 (a) It can be seen that both SA-PDI and GO / SA-PDI (80%) are composed of three elements: C, N, and O, while GO's main elemental composition is C and O. Figure 10 (b) It can be seen that the C1s spectrum of GO shows three peaks at 284.8 eV, 286.7 eV, and 287.8 eV, corresponding to C in C=C, CO, and C=O bonds, respectively; the C1s spectrum of SA-PDI shows four peaks at 284.8 eV, 286.3 eV, 287.8 eV, and 289.2 eV, corresponding to C in CC, CN, C=O, and π-exctiation bonds, respectively; the C1s spectrum of GO / SA-PDI (80%) shows... The 1s spectrum showed five peaks at 284.8 eV, 286.0 eV, 286.7 eV, 287.7 eV, and 289.2 eV, corresponding to C in the CC, CN, CO, C=O, and π-exctiation bonds, respectively. Compared with SA-PDI, the C=O and CN peaks in GO / SA-PDI (80%) shifted to lower binding energies, indicating a π-π interaction between SA-PDI and GO, leading to a change in electron density. Figure 10 (c) It can be seen that the N1s spectrum of SA-PDI only has a peak at 400.1 eV, and the GO / SA-PDI (80%) only has a peak at 400.2 eV, both corresponding to NC. x N in the bond; NC of GO / SA-PDI (80%) compared to SA-PDI x The shift of the peak to higher binding energies further indicates that there is electron transfer between GO and SA-PDI. Since GO itself has high conductivity, it is conducive to the transfer of photogenerated electrons generated by SA-PDI to GO, thereby improving the separation efficiency of photogenerated carriers in the composite material and enabling them to participate in the photocatalytic reaction process more quickly and effectively.

[0167] The diffuse reflectance (DRS) spectrum of the sample was measured using a UV-Vis spectrophotometer (Shimadzu UV-3600Plus). Figure 11 This is a comparison chart of the DRS of GO / SA-PDI (80%) prepared in Example 1, SA-PDI prepared in Comparative Example 1, and GO prepared in Comparative Example 2. Figure 11It is known that the spectral response range of SA-PDI almost covers the entire visible region, while the introduction of GO further enhances the light absorption capacity and light absorption range of GO / SA-PDI (80%) in the visible and near-infrared regions, further improving the utilization rate of sunlight by the composite material, thereby generating a greater number of photogenerated carriers to participate in the reaction.

[0168] Example 14 Photoelectric conversion performance test

[0169] Photoelectric conversion performance was tested on a CHI 660D electrochemical workstation (Chenhua Instrument). The standard three-electrode system included a counter electrode (platinum wire), a reference electrode (saturated calomel electrode), and a working electrode, with 0.1 mol / L Na₂SO₄ solution used as the electrolyte. The working electrode was prepared as follows: 5 mg of sample powder was ultrasonically dispersed in 1 mL of ultrapure water. The suspension was coated onto an indium tin oxide (ITO) glass surface, dried at room temperature, and heated at 180 °C for 5 h. A 300 W xenon lamp with a 400 nm cutoff filter was used as the visible light source. Photocurrent response was measured at 0.0 V; electrochemical impedance spectroscopy (EIS) was performed at 5 mV AC voltage from 0.01 Hz to 10 Hz. 5 Recorded within the Hz range.

[0170] Figure 12 This is a comparison of the photoelectric conversion performance of GO / SA-PDI (80%) prepared in Example 1 and SA-PDI prepared in Comparative Example 1. Figure 12 (a) It can be seen that GO / SA-PDI (80%) has a stronger photocurrent response value compared to SA-PDI, approximately 5.6 times that of SA-PDI. This indicates that the separation efficiency of photogenerated charges generated by GO / SA-PDI (80%) is significantly improved, allowing more photogenerated electrons to migrate from GO / SA-PDI (80%) to the ITO glass substrate. Figure 12(b) It can be seen that under both dark and light conditions, the radius of the arc of GO / SA-PDI (80%) is smaller than that of SA-PDI, indicating that its transfer resistance of photogenerated charges at the interface is lower, and the recombination probability of photogenerated electron-hole pairs is significantly suppressed. Compared with SA-PDI, GO / SA-PDI (80%) has a more outstanding photoelectric conversion capability. This is mainly because the introduction of highly conductive GO improves the separation and migration efficiency of photogenerated electrons and holes in the composite material. At the same time, the π-π interaction between GO and SA-PDI enhances the electron delocalization effect, which can promote the migration of photogenerated electrons in SA-PDI along the π-π stacking direction. Since the synthesis of H2O2 by GO / SA-PDI (80%) requires the reduction of O2 by photogenerated electrons, the performance of GO / SA-PDI (80%) in synthesizing H2O2 is stronger. Since the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) requires the reduction of Fe by photogenerated electrons, the GO / SA-PDI (80%) method is stronger. 3+ The photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) achieves the oxidation of pollutants through photogenerated holes, thus exhibiting stronger performance in removing organic matter, ARBs, and ARGs. It has been demonstrated that compared to the SA-PDI photocatalyst, the GO / SA-PDI (80%) synthesized photocatalyst possesses faster photogenerated carrier separation and migration rates, resulting in superior H2O2 synthesis and removal performance of organic matter, ARBs, and ARGs, making it a better carrier for constructing a photocatalytic self-Fenton synergistic reaction system.

[0171] Figure 13 This is a comparison of the degradation performance of sulfamethoxazole using the photocatalytic self-Fenton water treatment method (GO / SA-PDI(80%)-PSF) based on GO / SA-PDI(80%) in Example 7 after the addition of different active species capture agents. Figure 13 It can be seen that ammonium oxalate (AO), p-benzoquinone (p-BQ), and furfuryl alcohol (FFA) are used to capture photogenerated holes and ·O2, respectively. - and 1 The results of O2 and blank control groups showed that SMX had good stability under light irradiation. The addition of AO could significantly inhibit the degradation rate of SMX by the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%), while the addition of p-BQ and FFA had relatively low inhibitory effects on degradation performance. This indicates that photogenerated holes play a crucial role in the reaction process of the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%).

[0172] The electron spin resonance (ESR) spectra of the samples were measured using a Bruker EMXplus electron spin resonance spectrometer. Figure 14The ESR comparison charts show the photocatalytic water treatment methods based on GO / SA-PDI (80%) prepared in Example 1, the photocatalytic water treatment methods based on SA-PDI prepared in Comparative Example 1, and the photocatalytic self-Fenton water treatment method based on GO / SA-PDI (80%) in Example 7 (GO / SA-PDI (80%)-PSF). The signal of ·OH was detected in water using 5,5-dimethyl-1-pyrrolline-N-oxide (DMPO) as a spin probe. Figure 14 It can be seen that under visible light, the signal intensity of DMPO-·OH in GO / SA-PDI (80%) is stronger than that in SA-PDI, indicating that the composite system can generate more ·OH during photocatalysis. The addition of Fe... 3+ Subsequently, the ·OH signal intensity exhibited by the photocatalytic-self-Fenton system based on GO / SA-PDI (80%) was significantly improved compared to before its addition. This is attributed to the synergistic effect of photocatalytic self-Fenton, which effectively promotes the in-situ generation of H2O2 from GO / SA-PDI (80%) and the electron-reduced Fe. 2+ A self-Fenton reaction occurs between them, so the photocatalytic self-Fenton system based on GO / SA-PDI (80%) can generate more ·OH to participate in the oxidation reaction compared with the photocatalytic system.

Claims

1. An application of a photocatalytic self-Fenton water treatment method based on graphene oxide / self-assembled carboxylic acid perylene imide in the removal of sulfonamide resistance genes, characterized in that, The water treatment method is as follows: Add graphene oxide / self-assembled carboxyl perylene imide photocatalyst to the wastewater to be treated; adjust the pH and temperature of the reaction system; add Fe salt to the reaction system to construct a photocatalytic self-Fenton system; place the reaction system under a light source for irradiation; and continuously aerate to maintain oxygen saturation in the solution. The preparation method of the graphene oxide / self-assembled carboxyl perylene imide is as follows: Step 1: 3,4,9,10-perylenetetracarboxylic acid dianhydride, imidazole and β-aminopropionic acid are mixed and heated and stirred under inert gas protection. Alcohol and acid solution are added and stirred. After the reaction is completed, the mixture is separated, purified, dried and ground to prepare carboxyl perylene imide. Step 2: Disperse the carboxylated perylene imide in water, add an amine compound, heat and stir until the solid is completely dissolved, add an acid solution, heat and stir until precipitation stops, thus preparing a self-assembled carboxylated perylene imide dispersion, i.e., SA-PDI dispersion; the mass-to-volume ratio of the carboxylated perylene imide to water is 100:36.2 mg / mL; the mass-to-volume ratio of the carboxylated perylene imide to the amine compound is 100:151 mg / μL; the concentration of the acid solution is 4 mol / L; the mass-to-volume ratio of the carboxylated perylene imide to the acid solution is 100:4.7 mg / mL; the amine compound is triethylamine; the acid solution includes hydrochloric acid; Step 3: Disperse graphene oxide in water and sonicate to obtain GO dispersion; the mass-to-volume ratio of graphene oxide to water is 1 mg / mL. Step 4: Mix SA-PDI dispersion and GO dispersion. The mass ratio of graphene oxide to self-assembled carboxylated perylene imide is 1:

4. The mixture is ultrasonically treated, then heated and stirred. After the reaction is completed, the mixture is separated, purified, dried and ground to prepare graphene oxide / self-assembled carboxylated perylene imide, which is GO / SA-PDI photocatalyst. The mass ratio of the GO / SA-PDI photocatalyst to the Fe salt is 5:2, the pH of the reaction system is 6, and the reaction temperature is 25 °C; the light source is an LED lamp; the Fe salt is ferric chloride, ferric nitrate, or ferric sulfate.

2. The application of the photocatalytic self-Fenton water treatment method based on graphene oxide / self-assembled carboxylic acid perylene imide as described in claim 1 in the removal of sulfonamide resistance genes, characterized in that, In step 1 of the graphene oxide / self-assembly of carboxyl perylene imide: The inert gas mentioned includes argon, nitrogen, or helium; The alcohols mentioned include ethanol, methanol, or isopropanol; The acid solution includes hydrochloric acid, nitric acid, or sulfuric acid solution.

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