Soil organic pollutant photodegradation repairing agent as well as preparation method and application thereof
By using a monovalent copper-based coordination polymer photodegradation remediation agent, photocatalytic reaction is used to efficiently degrade chlortetracycline in the soil, solving the secondary pollution problem of traditional remediation methods and achieving efficient and stable chlortetracycline degradation.
Patent Information
- Application Number
- CN202510981420.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-16
- Publication Date
- 2025-11-11
AI Technical Summary
Existing technologies are insufficient for efficiently and environmentally friendly removal of chlortetracycline, an organic pollutant in soil, and traditional remediation methods may lead to secondary pollution.
The monovalent copper-based coordination polymer {[Cu(3-bbpa)0.5Cl]·2H2O}n is used as a photodegradation repair agent. The chlortetracycline is oxidized into harmless small molecules through photocatalytic reaction, avoiding the addition of chemical reagents and using light energy to drive the reaction.
It achieves efficient and stable photodegradation of chlortetracycline in soil, with high degradation efficiency and harmless small molecules as the products, which is in line with the concept of green and sustainable remediation and avoids secondary pollution.
Smart Images
Figure CN120923800A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of soil remediation agent technology, specifically relating to a photodegradation remediation agent for soil organic pollutants, its preparation method, and its application. Background Technology
[0002] Aureomycin, a tetracycline antibiotic, was once widely used in livestock and poultry farming to promote growth and prevent disease. However, its widespread use has led to drug residues entering water bodies and soil through feces and wastewater, causing ecological pollution. Aureomycin entering the soil can inhibit the activity of soil microorganisms and soil fertility, thus affecting crop growth. Photocatalytic degradation technology, due to its green, low-carbon, and highly efficient advantages, is gradually becoming a leading direction in the environmental field.
[0003] Coordination polymers, as functional materials, have demonstrated significant application value and development potential in energy conversion and environmental catalysis due to their unique coordination chemistry, tunable structure, and abundant catalytic active sites. Among them, copper-based coordination polymers show broad application prospects in photocatalysis. To date, research on the application of monovalent copper-based coordination polymers in photocatalytic environmental remediation is still very limited, indicating significant room for exploration and strong demand in this field. Therefore, developing photocatalytic degradation materials with high catalytic efficiency and good stability has become a key scientific issue in overcoming the challenges of treating chlortetracycline, an organic pollutant in soil. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides a photodegradation remediation agent for soil organic pollutants, its preparation method, and its application. This agent can efficiently degrade organic pollutants such as chlortetracycline compounds in soil, oxidizing them into harmless carbon dioxide and water. The degradation and removal process is driven solely by light energy, requiring no chemical reagents and avoiding secondary pollution that may occur with traditional remediation methods.
[0005] This invention is achieved by providing a photodegradation remediation agent for soil organic pollutants, wherein the molecular formula of the photodegradation remediation agent is {[Cu(3-bbpa)}. 0.5 Cl]·2H2O} n , where bbpa is N 1 N 4 -Di(3-pyridyl)succinamide, the structural formula of the photodegradation repair agent is:
[0006]
[0007] Preferably, the photodegradation repair agent has a triclinic crystal system and a space group of P–1.
[0008] Preferably, in the crystal structure of the photodegradation remediation agent, each monovalent copper ion is associated with N... 1 N 4 The 1-(3-pyridyl)succinamide ligand has a nitrogen atom connected to three coordinated chloride ions, forming a twisted tetragonal pyramidal geometry. 1 N 4 -Di(3-pyridyl)succinamide ligands bind adjacent [CuCl] n Subunits connect to form a one-dimensional chain, and then connect through hydrogen bonds to form a three-dimensional supramolecular structure.
[0009] Preferably, in the photodegradation remediation agent, the bond length of Cu(1)–N(1) is...
[0010] The bond length of Cu(1)–Cl(1)#1 is The bond angle of N(1)–Cu(1)–Cl(1) is 127.99(8). o The bond angle of Cl(1)–Cu(1)–Cl(1)#1 is 107.62(5). o .
[0011] A method for preparing the aforementioned photodegradation remediation agent for soil organic pollutants is provided, comprising the following steps:
[0012] Step 1: Weigh out copper chloride dihydrate and N2 by molar ratio. 1 N 4 -Di(3-pyridyl)succinamide and benzoic acid were added to the reaction vessel;
[0013] Step 2: Measure a certain volume of deionized water and sodium hydroxide solution and add them to the reaction vessel;
[0014] Step 3: Seal the reactor and crystallize it at a constant temperature in an oven for a certain time. Then, let it cool naturally to obtain yellow block crystals. Then, wash the block crystals with deionized water, filter and dry them to obtain a photodegradation remediation agent for soil organic pollutants.
[0015] Preferably, in step 1, copper chloride dihydrate, benzoic acid, and N... 1 N 4 The molar ratio of bis(3-pyridyl)succinamide is 1–2:1.5:1–2.
[0016] Preferably, in step 2, the volume ratio of deionized water to sodium hydroxide solution is 6:1, and the concentration of sodium hydroxide solution is 0.2 mol / L.
[0017] Preferably, in step 3, the oven temperature is 120–140°C and the crystallization time is 3–5 days.
[0018] This invention provides an application of the aforementioned photodegradation remediation agent for soil organic pollutants, specifically for the remediation of paddy soil containing the organic pollutant antibiotic chlortetracycline.
[0019] The photodegradation remediation agent for soil organic pollutants provided by this invention is a green technology that utilizes light energy to drive a chemical reaction to degrade pollutants. It has the following significant advantages: 1. High degradation efficiency: It can rapidly decompose organic pollutants such as chlortetracycline in the soil. By optimizing the particle size and specific surface area of the photodegradation agent, the active sites can be increased, further improving the degradation efficiency. Furthermore, the photocatalyst has strong regeneration capabilities, high long-term stability, and can sustainably function. 2. Environmentally friendly: The reaction process relies solely on light energy, requiring no chemical reagents, thus avoiding secondary pollution that may occur with traditional remediation methods. The degradation products are mainly harmless small molecules (carbon dioxide and water), conforming to the concept of green and sustainable remediation. Attached Figure Description
[0020] Figure 1 Structural diagram of a photodegradation remediation agent for soil organic pollutants;
[0021] Figure 2 This is a three-dimensional supramolecular structure of a photodegradation remediation agent for soil organic pollutants (red represents oxygen atoms, black dashed lines represent hydrogen bonds, and other colors represent nitrogen). 1 N 4 -Di(3-pyridyl)succinamide (one-dimensional chain);
[0022] Figure 3 A comparison of powder X-ray diffraction pattern and single-crystal data simulation for a photodegradation remediation agent for soil organic pollutants;
[0023] Figure 4 A curve showing the removal of chlortetracycline by a photodegradable remediation agent for soil organic pollutants in a simulated aqueous solution;
[0024] Figure 5 A bar chart showing the remediation effect of a photodegradation remediation agent for soil organic pollutants on simulated soil containing chlortetracycline. Detailed Implementation
[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0026] Example 1
[0027] Add 0.034 g (0.20 mmol) of CuCl2·2H2O and 0.027 g (0.10 mmol) of N2O. 1 N4 3-Bis(3-pyridyl)succinamide, 0.018 g (0.15 mmol) of benzoic acid, 1 mL of 0.2 M NaOH, and 6 mL of deionized water were mixed in a high-pressure reactor lined with polytetrafluoroethylene (PTFE), and the reactor was heated in an oven at 130 °C for 4 days. Subsequently, the oven was allowed to cool naturally to 25 °C, yielding yellow blocky crystals in a yield of 56.2%.
[0028] Example 2
[0029] Add 0.017 g (0.10 mmol) of CuCl2·2H2O and 0.027 g (0.10 mmol) of N2O. 1 N 4 3-Bis(3-pyridyl)succinamide, 0.018 g (0.15 mmol) of benzoic acid, 1 mL of 0.2 M NaOH, and 6 mL of water were mixed in a high-pressure reactor lined with polytetrafluoroethylene (PTFE), and the reactor was heated in an oven at 130 °C for 4 days. Subsequently, the oven was allowed to cool naturally to 25 °C, yielding yellow blocky crystals in a yield of 55.1%.
[0030] Example 3
[0031] Add 0.017 g (0.10 mmol) of CuCl2·2H2O and 0.054 g (0.20 mmol) of N2O. 1 N 4 3-Bis(3-pyridyl)succinamide, 0.018 g (0.15 mmol) of benzoic acid, 1 mL of 0.2 M NaOH, and 6 mL of water were mixed in a high-pressure reactor lined with polytetrafluoroethylene (PTFE), and the reactor was heated in an oven at 130 °C for 4 days. Subsequently, the oven was allowed to cool naturally to 25 °C, yielding yellow blocky crystals in a yield of 55.3%.
[0032] Example 4
[0033] Add 0.034 g (0.20 mmol) of CuCl2·2H2O and 0.027 g (0.10 mmol) of N2O. 1 N 4 3-Bis(3-pyridyl)succinamide, 0.018 g (0.15 mmol) of benzoic acid, 1 mL of 0.2 M NaOH, and 6 mL of water were mixed in a high-pressure reactor lined with polytetrafluoroethylene (PTFE), and the reactor was heated in an oven at 120 °C for 4 days. Subsequently, the oven was allowed to cool naturally to 25 °C, yielding yellow blocky crystals in a yield of 53.4%.
[0034] Example 5
[0035] Add 0.034 g (0.20 mmol) of CuCl2·2H2O and 0.027 g (0.10 mmol) of N2O. 1 N 4 3-Bis(3-pyridyl)succinamide, 0.018 g (0.15 mmol) of benzoic acid, 1 mL of 0.2 M NaOH, and 6 mL of water were mixed in a polytetrafluoroethylene-lined autoclave and heated in an oven at 140 °C for 4 days. The oven was then allowed to cool naturally to 25 °C, yielding yellow blocky crystals in 50.7% yield.
[0036] Example 6
[0037] Add 0.034 g (0.20 mmol) of CuCl2·2H2O and 0.027 g (0.10 mmol) of N2O. 1 N 4 3-Bis(3-pyridyl)succinamide, 0.018 g (0.15 mmol) of benzoic acid, 1 mL of 0.2 M NaOH, and 6 mL of water were mixed in a high-pressure reactor lined with polytetrafluoroethylene (PTFE), and the reactor was heated in an oven at 130 °C for 3 days. Subsequently, the oven was allowed to cool naturally to 25 °C, yielding yellow blocky crystals in a yield of 51.2%.
[0038] Example 7
[0039] Add 0.034 g (0.20 mmol) of CuCl2·2H2O and 0.027 g (0.10 mmol) of N2O. 1 N 4 3-Bis(3-pyridyl)succinamide, 0.018 g (0.15 mmol) of benzoic acid, 1 mL of 0.2 M NaOH, and 6 mL of water were mixed in a high-pressure reactor lined with polytetrafluoroethylene (PTFE), and the reactor was heated in an oven at 130 °C for 5 days. Subsequently, the oven was allowed to cool naturally to 25 °C, yielding yellow blocky crystals in a yield of 54.9%.
[0040] Examples 1–7 yielded photodegradation remediation agents for the same type of soil organic pollutants, with the optimal yield achieved using the proportions of Example 1.
[0041] Determination of the structure of novel photodegradation remediation agents for soil organic pollutants: Graphite monochromatography was performed on a Bruker D8 X-ray diffractometer. Radiation was used as the diffraction source to collect diffraction intensity data of the yellow bulk crystal single crystal prepared in Example 1. Specific crystallographic parameters are shown in Table 1. Further structural diagrams are shown below. Figure 1 As shown. Figure 1 The display shows monovalent copper ions and N 1 N 4One nitrogen atom in the bis(3-pyridyl)succinamide ligand is linked to three coordinated chloride ions to form a distorted tetragonal pyramidal geometry. Figure 2 N 1 N 4 -Di(3-pyridyl)succinamide ligands bind adjacent [CuCl] n Subunits connect to form a one-dimensional chain, and then are linked by hydrogen bonds to form a three-dimensional supramolecular structure. The bond length of Cu(1)–N(1) is...
[0042] The bond length of Cu(1)–Cl(1)#1 is The bond angle of N(1)–Cu(1)–Cl(1) is 127.99(8). o The bond angle of Cl(1)–Cu(1)–Cl(1)#1 is 107.62(5). o .
[0043] Table 1. Crystallographic parameters of a photodegradation remediation agent for soil organic pollutants.
[0044]
[0045]
[0046] Powder diffraction experiments were performed on the crystal using a Bruker D8 Advance X-ray powder diffractometer: graphite monochromatized Cu Kα radiation was used, wavelength... Solid-state detector, step size 0.01°, step time 0.3s, scanning range 10°≤2θ≤60°. The powder X-ray diffraction pattern obtained in Example 1 matches the simulation pattern obtained from single-crystal data. Figure 3 ).
[0047] 1. Degradation and removal effect in simulated solution
[0048] In simulated aqueous solutions, the photocatalytic purification performance of photodegradable remediation materials for chlortetracycline contaminants was tested under sunlight irradiation. For example... Figure 4 As shown, the dark reaction adsorption results indicate that neither the ligand nor the remediation agent exhibits adsorption performance for chlortetracycline contaminants. Notably, the photodegradation remediation agent demonstrates excellent photocatalytic performance, achieving a chlortetracycline degradation efficiency of 92.41% after 80 minutes of exposure to sunlight. It is worth mentioning that the photocatalytic performance of the photodegradation remediation agent is far superior to previously reported materials (see Table 2).
[0049] Table 2 compares the degradation effect of the remedial agent of the present invention on chlortetracycline with other remedial agents.
[0050]
[0051]
[0052] 2. Simulating the remediation effect of chlortetracycline containing organic matter in soil.
[0053] The new material was further studied as a photodegradation remediation agent for soil organic pollutants. Soil samples containing chlortetracycline were artificially added using paddy field soil. 100g of contaminated soil was mixed with 200mL of water to form a homogeneous slurry suspension. After the suspension settled, the soil photodegradation remediation agent was added to the surface and evenly dispersed. The slurry was placed at a cement interface for light treatment, and samples were collected daily for seven consecutive days. The experiment was conducted under natural light and a xenon lamp as a control. Monitoring results showed that under xenon lamp irradiation, the degradation efficiency of chlortetracycline gradually increased from 25.52% to 96.44%; while under natural light irradiation, the degradation efficiency gradually increased from 23.65% to 79.96%, which was attributed to the weaker intensity of natural light. Figure 5 Experimental results show that the material of this invention is a potential soil remediation agent for the degradation of organic pollutants in soil.
Claims
1. A photodegradation remediation agent for soil organic pollutants, characterized in that, The molecular formula of the photodegradation remediation agent is {[Cu(3-bbpa)}. 0.5 Cl]·2H2O} n , where bbpa is N 1 N 4 -Di(3-pyridyl)succinamide, the structural formula of the photodegradation repair agent is:
2. The soil organic pollutant photodegradation remediation agent according to claim 1, characterized in that, The photodegradation repair agent has a triclinic crystal system and a space group of P–1.
3. The photodegradation remediation agent for soil organic pollutants according to claim 1, characterized in that, In the crystal structure of the photodegradation repair agent, each monovalent copper ion is associated with N. 1 N 4 The 1-(3-pyridyl)succinamide ligand has a nitrogen atom connected to three coordinated chloride ions, forming a twisted tetragonal pyramidal geometry. 1 N 4 -Di(3-pyridyl)succinamide ligands bind adjacent [CuCl] n Subunits connect to form a one-dimensional chain, and then connect through hydrogen bonds to form a three-dimensional supramolecular structure.
4. The soil organic pollutant photodegradation remediation agent according to claim 1, characterized in that, In the photodegradation remediation agent, the bond length of Cu(1)–N(1) is... The bond length of Cu(1)–Cl(1)#1 is The bond angle of N(1)–Cu(1)–Cl(1) is 127.99(8). o The bond angle of Cl(1)–Cu(1)–Cl(1)#1 is 107.62(5). o .
5. A method for preparing a soil organic pollutant photodegradation remediation agent according to any one of claims 1-4, characterized in that, Includes the following steps: Step 1: Weigh out copper chloride dihydrate and N2 by molar ratio. 1 N 4 -Di(3-pyridyl)succinamide and benzoic acid were added to the reaction vessel; Step 2: Measure a certain volume of deionized water and sodium hydroxide solution and add them to the reaction vessel; Step 3: Seal the reactor and crystallize it at a constant temperature in an oven for a certain time. Then, let it cool naturally to obtain yellow block crystals. Then, wash the block crystals with deionized water, filter and dry them to obtain a photodegradation remediation agent for soil organic pollutants.
6. The method for preparing the photodegradation remediation agent for soil organic pollutants according to claim 5, characterized in that, In step 1, copper chloride dihydrate, benzoic acid, and N... 1 N 4 The molar ratio of bis(3-pyridyl)succinamide is 1–2:1.5:1–2.
7. The preparation method of the photodegradation remediation agent for soil organic pollutants according to claim 5, characterized in that, In step 2, the volume ratio of deionized water to sodium hydroxide solution is 6:1, and the concentration of sodium hydroxide solution is 0.2 mol / L.
8. The method for preparing the photodegradation remediation agent for soil organic pollutants according to claim 5, characterized in that, In step 3, the oven temperature is 120–140℃ and the crystallization time is 3–5 days.
9. The application of the photodegradation remediation agent for soil organic pollutants according to any one of claims 1–4, characterized in that, As a photodegradation remediation agent for organic pollutants in agricultural soil, it is applied to the remediation of paddy soil containing the organic pollutant antibiotic chlortetracycline.