A method and application for controlling the bending degree of two-dimensional cobalt tetracoordinate conjugated compounds in three-dimensional tubular carbon materials.
By using a composite structure of three-dimensional honeycomb tubular carbon material and two-dimensional cobalt four-coordinate conjugated system compound, the degree of bending strain can be controlled, which solves the problem of difficulty in controlling the bending strain of two-dimensional cobalt four-coordinate conjugated system compound in the prior art, and improves its performance in activating persulfate degradation of pollutants in catalytic reactions.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ZHEJIANG UNIV OF TECH
- Filing Date
- 2024-02-29
- Publication Date
- 2026-05-26
AI Technical Summary
Existing technologies cannot effectively control the degree of bending strain of two-dimensional cobalt tetracoordinate conjugated system compounds on three-dimensional tubular carbon materials, which affects their electron transfer tendency and catalytic performance in catalytic reactions.
By utilizing π-π interactions, a composite structure is formed by three-dimensional honeycomb tubular carbon materials and two-dimensional cobalt four-coordinate conjugated system compounds. The bending degree of the two-dimensional cobalt four-coordinate structure is controlled, avoiding high temperature or acid intervention, and its bending configuration is controlled by a simple method.
The bending strain regulation of two-dimensional cobalt four-coordinate conjugated system compounds on three-dimensional honeycomb tubular carbon materials was realized, which enhanced their performance in activating persulfate degradation of pollutants and showed high catalytic activity and stability.
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Figure CN118289740B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of materials preparation, and particularly relates to a method and application for regulating the bending degree of a two-dimensional cobalt tetracoordinate conjugated compound in a three-dimensional tubular carbon material. Background Technology
[0002] Two-dimensional cobalt four-coordinate conjugated compounds, with their unique metallic four-coordinate structure, have been extensively studied for their twisting of the metal center and corresponding changes in electronic structure, demonstrating outstanding performance in catalysis. The twisted configuration of the metal center, as the reaction site, has a profound impact on its electronic structure, thereby altering the electron transfer tendency of the reaction site in catalytic reactions. Existing techniques have demonstrated that in Ru single-atom catalysts of molybdenum disulfide, fine-tuning of the strain at the reaction site enhances the synergistic interaction between sulfur vacancies and Ru sites. This enhancement promotes efficient electron transfer to Ru sites, thereby accelerating the reaction process at the catalytic site (Jiang K, Luo M, Liu Z et al. Rationalstrain engineering of single-atom ruthenium on nanoporous MoS2 for highly efficient hydrogen evolution. Nat. Commun. 2021, 12, 1687). Optimization of this strain engineering offers the potential to control electron transfer tendency, providing a method for improving the redox potential of reactants. However, achieving different degrees of bending strain remains a considerable technical challenge.
[0003] Therefore, researchers in the environmental field have begun to modify materials through bending strain to obtain two-dimensional cobalt four-coordinate conjugated system compounds with enhanced catalytic performance for pollution control applications. In existing technologies, modification is typically achieved through calcination, acid treatment, etc., while this invention requires no high temperature or acid intervention, making it clean and environmentally friendly. Therefore, controlling the degree of bending strain in two-dimensional cobalt four-coordinate conjugated system compounds using safe and environmentally friendly methods is crucial. Summary of the Invention
[0004] To address the aforementioned technical problems in existing technologies, the present invention aims to provide a method and application for controlling the bending degree of a two-dimensional cobalt four-coordinate conjugated compound in a three-dimensional tubular carbon material. The method of the present invention controls the bending strain of a two-dimensional cobalt four-coordinate conjugated compound in a three-dimensional honeycomb tubular carbon material using a simple approach. The resulting composite material of the two-dimensional cobalt four-coordinate conjugated compound and the three-dimensional honeycomb tubular carbon material exhibits high activity in activating persulfate degradation of pollutants.
[0005] To control the bending strain of a two-dimensional cobalt four-coordinate conjugated system compound on a three-dimensional honeycomb tubular carbon material, this invention employs a novel approach: both the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material possess conjugated structures, which can combine with each other through π-π interactions to form a composite structure; the three-dimensional honeycomb tubular carbon material can exert a force on the two-dimensional cobalt four-coordinate conjugated system compound on its surface through π-π interactions, bending its configuration; by changing the diameter of the three-dimensional honeycomb tubular carbon material, the bending degree of the two-dimensional cobalt four-coordinate conjugated system compound can be controlled.
[0006] The specific technical solution is as follows:
[0007] A method for controlling the bending degree of a two-dimensional cobalt tetracoordinated conjugated compound in a three-dimensional tubular carbon material, comprising the following steps:
[0008] 1) The three-dimensional honeycomb tubular carbon material was uniformly dispersed in methanol by ultrasound, and then the dispersion of the three-dimensional honeycomb tubular carbon material was magnetically stirred.
[0009] 2) The two-dimensional cobalt four-coordinate conjugated system compound was dispersed in methanol by stirring to form a uniform two-dimensional cobalt four-coordinate conjugated system compound dispersion;
[0010] 3) The two-dimensional cobalt tetracoordinate structure conjugated system compound dispersion obtained in step 2) is added dropwise to the three-dimensional honeycomb tubular carbon material dispersion obtained in step 1), and the dispersion is kept magnetically stirred for 12-48 hours.
[0011] 4) After stirring, the black solid obtained by filtration is washed with methanol to remove excess two-dimensional cobalt four-coordinate conjugated system compound. The obtained solid is dried in a vacuum drying oven for 4-48 hours to obtain a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material composite structure.
[0012] Furthermore, in step 1), the diameter of the three-dimensional honeycomb tubular carbon material is 4-30 nm, preferably 4-6 nm, and the length is 10-30 μm.
[0013] Further, in step 1), the mass ratio of the three-dimensional honeycomb tubular carbon material to the volume ratio of methanol is 50-200:50-200, where the mass unit is mg and the volume unit is mL, preferably 100:100.
[0014] Further, in step 2), the mass-to-volume ratio of the conjugated system compound with the two-dimensional cobalt tetracoordinate structure to methanol is 2-20:20-150, where the mass unit is mg and the volume unit is mL, preferably 6:50.
[0015] Further, in step 3), the volume ratio of the two-dimensional cobalt four-coordinate conjugated system compound dispersion and the three-dimensional honeycomb tubular carbon material dispersion is 1:1-3, preferably 1:2.
[0016] Further, in step 4), the drying temperature in the vacuum drying oven is 50-80℃, preferably 60℃, and the drying time is 4-24h, preferably 8h.
[0017] A composite structure of a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material prepared by the above method.
[0018] The application of a composite structure of a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material in the degradation of pollutants by activated persulfate involves adding the composite structure of the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material to an aqueous solution of pollutants, followed by the addition of persulfate after stirring. The resulting mixed solution is then subjected to pollutant degradation under stirring. The mass ratio of the composite structure of the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material to the mass of persulfate is 2–50:10–30.
[0019] Compared with the prior art, the present invention achieves the following technical effects:
[0020] 1) This invention provides a method for controlling the bending strain of a two-dimensional cobalt four-coordinate conjugated system compound on a three-dimensional honeycomb tubular carbon material. This method enables the two-dimensional cobalt four-coordinate conjugated system compound to have a bent metal center configuration, thereby enhancing its performance in activating persulfate degradation of pollutants. The composite structure material of the two-dimensional cobalt four-coordinate conjugated system compound with a bent configuration and the three-dimensional honeycomb tubular carbon material of this invention has a simple, efficient, and low-cost preparation method. At the same time, by adjusting the diameter of the three-dimensional honeycomb tubular carbon material, the bending strain of the two-dimensional cobalt four-coordinate conjugated system compound can be controlled, thereby controlling its performance in activating persulfate degradation of pollutants.
[0021] 2) The composite structure material synthesized in this invention, which is a conjugated system compound with a curved two-dimensional cobalt four-coordinate structure and a three-dimensional honeycomb tubular carbon material, exhibits extremely high catalytic performance for activating persulfate. In the preparation method of this invention, the composite structure is constructed by utilizing π-π interactions, which avoids breaking the metal central coordination bonds of the conjugated system compound with a two-dimensional cobalt four-coordinate structure, so that the catalyst structure has both good catalytic activity and stability. Attached Figure Description
[0022] Figure 1The image shows a transmission electron microscope (TEM) scan of the composite structure of the two-dimensional cobalt tetracoordinate conjugated system compound with a curved configuration and the three-dimensional honeycomb tubular carbon material prepared in Example 1.
[0023] Figure 2 The image shows a transmission electron microscope (TEM) scan of the composite structure of the two-dimensional cobalt tetracoordinate conjugated system compound with a curved configuration and the three-dimensional honeycomb tubular carbon material prepared in Example 2.
[0024] Figure 3 The image shows a transmission electron microscope (TEM) scan of the composite structure of the two-dimensional cobalt tetracoordinate conjugated system compound with a curved configuration and the three-dimensional honeycomb tubular carbon material prepared in Example 3.
[0025] Figure 4 The image shows a transmission electron microscope (TEM) scan of the composite structure of the two-dimensional cobalt tetracoordinate conjugated system compound with a curved configuration and the three-dimensional honeycomb tubular carbon material prepared in Example 4.
[0026] Figure 5 This is a schematic diagram of a conjugated system compound with a two-dimensional cobalt four-coordinate structure bending on the surface of a three-dimensional honeycomb tubular carbon material. Detailed Implementation
[0027] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.
[0028] Example 1
[0029] In this embodiment, the specific steps for preparing the composite structural material of the synthesized two-dimensional cobalt four-coordinate conjugated system compound with a curved configuration and a three-dimensional honeycomb tubular carbon material are as follows:
[0030] (1) 100 mg of three-dimensional honeycomb tubular carbon material with a diameter of 2-4 nm and a length of 10-30 μm was uniformly dispersed in 100 mL of methanol by ultrasonication, and then the dispersion of the three-dimensional honeycomb tubular carbon material was magnetically stirred.
[0031] (2) 6 mg of the two-dimensional cobalt four-coordinate conjugated system compound was dispersed in 50 mL of methanol by stirring to form a uniform two-dimensional cobalt four-coordinate conjugated system compound dispersion.
[0032] (3) Slowly drop the 50 mL two-dimensional cobalt tetracoordinate conjugated system compound dispersion obtained in step 2) into the 100 mL three-dimensional honeycomb tubular carbon material dispersion obtained in step 1), and keep the dispersion magnetically stirred for 24 hours.
[0033] (4) After stirring, the black solid obtained by filtration was washed three times with methanol to remove excess two-dimensional cobalt four-coordinate conjugated system compound. The obtained solid was dried in a vacuum drying oven at 60°C for 8 hours to obtain a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material composite material.
[0034] Example 2
[0035] (1) 100 mg of three-dimensional honeycomb tubular carbon material with a diameter of 4-6 nm and a length of 10-30 μm was uniformly dispersed in 100 mL of methanol by ultrasonication, and then the dispersion of the three-dimensional honeycomb tubular carbon material was magnetically stirred.
[0036] (2) 6 mg of the two-dimensional cobalt four-coordinate conjugated system compound was dispersed in 50 mL of methanol by stirring to form a uniform two-dimensional cobalt four-coordinate conjugated system compound dispersion.
[0037] (3) Slowly drop the 50 mL two-dimensional cobalt tetracoordinate conjugated system compound dispersion obtained in step 2) into the 100 mL three-dimensional honeycomb tubular carbon material dispersion obtained in step 1), and keep the dispersion magnetically stirred for 24 hours.
[0038] (4) After stirring, the black solid obtained by filtration was washed three times with methanol to remove excess two-dimensional cobalt four-coordinate conjugated system compound. The obtained solid was dried in a vacuum drying oven at 60°C for 8 hours to obtain a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material composite material.
[0039] Example 3
[0040] (1) 100 mg of three-dimensional honeycomb tubular carbon material with a diameter of 8-15 nm and a length of 10-30 μm was uniformly dispersed in 100 mL of methanol by ultrasonication, and then the dispersion of the three-dimensional honeycomb tubular carbon material was magnetically stirred.
[0041] (2) 6 mg of the two-dimensional cobalt four-coordinate conjugated system compound was dispersed in 50 mL of methanol by stirring to form a uniform two-dimensional cobalt four-coordinate conjugated system compound dispersion.
[0042] (3) Slowly drop the 50 mL two-dimensional cobalt tetracoordinate conjugated system compound dispersion obtained in step 2) into the 100 mL three-dimensional honeycomb tubular carbon material dispersion obtained in step 1), and keep the dispersion magnetically stirred for 24 hours.
[0043] (4) After stirring, the black solid obtained by filtration was washed three times with methanol to remove excess two-dimensional cobalt four-coordinate conjugated system compound. The obtained solid was dried in a vacuum drying oven at 60°C for 8 hours to obtain a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material composite material.
[0044] Example 4
[0045] (1) 100 mg of three-dimensional honeycomb tubular carbon material with a diameter of 20-30 nm and a length of 10-30 μm was uniformly dispersed in 100 mL of methanol by ultrasonication, and then the dispersion of the three-dimensional honeycomb tubular carbon material was magnetically stirred.
[0046] (2) 6 mg of the two-dimensional cobalt four-coordinate conjugated system compound was dispersed in 50 mL of methanol by stirring to form a uniform two-dimensional cobalt four-coordinate conjugated system compound dispersion.
[0047] (3) Slowly drop the 50 mL two-dimensional cobalt tetracoordinate conjugated system compound dispersion obtained in step 2) into the 100 mL three-dimensional honeycomb tubular carbon material dispersion obtained in step 1), and keep the dispersion magnetically stirred for 24 hours.
[0048] (4) After stirring, the black solid obtained by filtration was washed three times with methanol to remove excess two-dimensional cobalt four-coordinate conjugated system compound. The obtained solid was dried in a vacuum drying oven at 60°C for 8 hours to obtain a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material composite material.
[0049] Example 5
[0050] (1) 100 mg of three-dimensional honeycomb tubular carbon material with a diameter of 30-50 nm and a length of 10-30 μm was uniformly dispersed in 100 mL of methanol by ultrasonication, and then the dispersion of the three-dimensional honeycomb tubular carbon material was magnetically stirred.
[0051] (2) 6 mg of the two-dimensional cobalt four-coordinate conjugated system compound was dispersed in 50 mL of methanol by stirring to form a uniform two-dimensional cobalt four-coordinate conjugated system compound dispersion.
[0052] (3) Slowly drop the 50 mL two-dimensional cobalt tetracoordinate conjugated system compound dispersion obtained in step 2) into the 100 mL three-dimensional honeycomb tubular carbon material dispersion obtained in step 1), and keep the dispersion magnetically stirred for 24 hours.
[0053] (4) After stirring, the black solid obtained by filtration was washed three times with methanol to remove excess two-dimensional cobalt four-coordinate conjugated system compound. The obtained solid was dried in a vacuum drying oven at 60°C for 8 hours to obtain a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material composite material.
[0054] Example 6
[0055] (1) 100 mg of three-dimensional honeycomb tubular carbon material with a diameter greater than 50 nm and a length of 10-30 μm was uniformly dispersed in 100 mL of methanol by ultrasonication, and then the dispersion of the three-dimensional honeycomb tubular carbon material was magnetically stirred.
[0056] (2) 6 mg of the two-dimensional cobalt four-coordinate conjugated system compound was dispersed in 50 mL of methanol by stirring to form a uniform two-dimensional cobalt four-coordinate conjugated system compound dispersion.
[0057] (3) Slowly drop the 50 mL two-dimensional cobalt tetracoordinate conjugated system compound dispersion obtained in step 2) into the 100 mL three-dimensional honeycomb tubular carbon material dispersion obtained in step 1), and keep the dispersion magnetically stirred for 24 hours.
[0058] (4) After stirring, the black solid obtained by filtration was washed three times with methanol to remove excess two-dimensional cobalt four-coordinate conjugated system compound. The obtained solid was dried in a vacuum drying oven at 60°C for 8 hours to obtain a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material composite material.
[0059] Transmission electron microscopy (TEM) scans were performed on the two-dimensional cobalt tetracoordinate conjugated system compounds and the three-dimensional honeycomb tubular carbon composite materials obtained in Examples 1, 2, 3, and 4. The results are as follows: Figure 1 , Figure 2 , Figure 3 , Figure 4 As shown.
[0060] Application Example 1:
[0061] The two-dimensional cobalt four-coordinate conjugated system compounds obtained in Examples 1-6 and the three-dimensional honeycomb tubular carbon material composite material were used to conduct experiments on the degradation of pollutants by activated persulfate.
[0062] The experimental conditions were as follows: 5 mg of the two-dimensional cobalt tetracoordinate conjugated system compound and the three-dimensional honeycomb tubular carbon composite material obtained in Examples 1-6 were measured into a beaker containing 100 mL of a 5 mg / L pollutant solution. 10 mg of persulfate was added to the beaker, and the mixture was stirred at 250 rpm to degrade the pollutants. Samples were taken periodically after 5 min of reaction, and the gas concentration in the reactor was detected by gas chromatography. The results are shown in Table 1.
[0063] Table 1. Degradation rates of bisphenol A pollutants within 5 min for activated persulfate composite materials with two-dimensional cobalt tetracoordinate structures and three-dimensional honeycomb tubular carbon materials.
[0064]
[0065] As shown in Table 1, the composite material of the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material synthesized in this invention exhibits excellent catalytic activity for the degradation of pollutants by activated persulfate. In Examples 1-6, during the preparation of the composite material of the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material, the smaller the diameter of the three-dimensional honeycomb tubular carbon material, the more pronounced the tortuosity of the two-dimensional cobalt four-coordinate conjugated system compound became, while the degradation of bisphenol A by activated persulfate initially increased and then decreased.
[0066] Using the sample obtained in Example 2, a cyclic test was conducted under the same experimental conditions as described above. After four cycles, the pollutant degradation rate of the sample obtained in Example 2 was 90%, which remained at a very high level, indicating that the catalyst has good stability.
[0067] Table 2. Summary of bond length variations of conjugated system compounds with two-dimensional cobalt four-coordinate structures on the surface of tubular carbon materials with different three-dimensional honeycomb configurations.
[0068]
[0069]
[0070] Comparison Figure 1 The three-dimensional honeycomb tubular carbon materials have small tube diameters, and Table 2 shows that the Co-N bond lengths are short, resulting in a stronger degree of bending strain in the conjugated system compounds of the two-dimensional cobalt tetracoordinate structure on the surface. Figure 5 As shown in the figure, the π band at the metal center is less broadened, the electron vacancy rate is lower, and the redox potential of the complex formed by the material and monopersulfate is lower, resulting in a lower pollutant degradation rate.
[0071] Comparison Figure 2The tubular carbon material with a three-dimensional honeycomb structure has a moderate tube diameter, and Table 2 shows that the Co-N bond length is moderate. This results in a moderate degree of bending strain in the conjugated system compound of the two-dimensional cobalt four-coordinate structure on the surface, which leads to a greater degree of π band broadening in the metal center and a higher electron vacancy rate. Consequently, the redox potential of the complex formed by the material and monopersulfate increases, and the pollutant degradation rate is higher.
[0072] Comparison Figure 3 The tubular carbon material with a three-dimensional honeycomb structure has a large diameter, and as shown in Table 2, the Co-N bond length is relatively long. This results in a smaller degree of bending strain in the conjugated system compound of the two-dimensional cobalt four-coordinate structure on the surface, which leads to a smaller degree of π band broadening in the metal center and a lower electron vacancy rate. Consequently, the redox potential of the complex formed by the material and monopersulfate decreases, and the degradation rate of pollutants decreases.
[0073] Comparison Figure 4 The tubular carbon material with a three-dimensional honeycomb structure has a larger diameter, and Table 2 shows that the Co-N bond length is longer. This results in a smaller degree of bending strain in the conjugated system compound of the two-dimensional cobalt four-coordinate structure on the surface, which further reduces the broadening of the π band in the metal center and lowers the electron vacancy rate. Consequently, the redox potential of the complex formed by the material and monopersulfate decreases, and the degradation rate of pollutants further decreases.
[0074] This demonstrates that the composite material of the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material exhibits extremely high efficiency in activating persulfate degradation of pollutants, and its degradation efficiency can be adjusted by regulating the diameter of the three-dimensional honeycomb tubular carbon material. After several rounds of cyclic experiments, the composite material of the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material still possesses high catalytic activity.
[0075] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the invention. For example, although a two-dimensional cobalt four-coordinate conjugated system compound was used in the preparation process in the above embodiments, it does not mean that a two-dimensional cobalt four-coordinate conjugated system compound must be used. Similarly, two-dimensional iron four-coordinate conjugated system compounds and two-dimensional copper four-coordinate conjugated system compounds can also achieve the effects of the present invention. Furthermore, in the preparation process, the three-dimensional honeycomb tubular carbon material and the two-dimensional cobalt four-coordinate conjugated system compound are dispersed in methanol, but this does not mean that they must be dispersed in methanol. Similarly, organic solvents such as N,N-dimethylformamide can be used instead, as long as the three-dimensional honeycomb tubular carbon material and the two-dimensional cobalt four-coordinate conjugated system compound are uniformly dispersed, allowing them to form a composite structure through π-π interactions, the effects of the present invention can be achieved.
[0076] The contents described in this specification are merely an enumeration of the implementation forms of the inventive concept, and the scope of protection of this invention should not be regarded as limited to the specific forms described in the embodiments.
Claims
1. A method for controlling the degree of bending of a two-dimensional cobalt tetracoordinate conjugated compound in a three-dimensional tubular carbon material, characterized in that, Includes the following steps: 1) The three-dimensional honeycomb tubular carbon material was uniformly dispersed in methanol by ultrasound, and then the dispersion of the three-dimensional honeycomb tubular carbon material was magnetically stirred. 2) The two-dimensional cobalt four-coordinate conjugated system compound was dispersed in methanol by stirring to form a uniform two-dimensional cobalt four-coordinate conjugated system compound dispersion; 3) The two-dimensional cobalt tetracoordinate structure conjugated system compound dispersion obtained in step 2) is added dropwise to the three-dimensional honeycomb tubular carbon material dispersion obtained in step 1), and the dispersion is kept magnetically stirred for 12-48 hours. 4) After stirring, the black solid obtained by filtration is washed with methanol to remove excess two-dimensional cobalt four-coordinate conjugated system compound. The obtained solid is dried in a vacuum drying oven for 4-48 hours to obtain two-dimensional cobalt four-coordinate conjugated system compound and three-dimensional honeycomb tubular carbon material composite structure. By adjusting the diameter of the added three-dimensional honeycomb tubular carbon material, the degree of bending of the two-dimensional cobalt tetracoordinate conjugated compound on the three-dimensional tubular carbon material can be changed.
2. The method as described in claim 1, characterized in that, The diameter of the three-dimensional honeycomb tubular carbon material in step 1) is 4-30 nm and the length is 10-30 μm.
3. The method as described in claim 2, characterized in that, The diameter of the three-dimensional honeycomb tubular carbon material in step 1) is 4-6 nm.
4. The method as described in claim 1, characterized in that, The mass ratio of the three-dimensional honeycomb tubular carbon material to the volume of methanol in step 1) is 50-200 : 50-200, with mass in mg and volume in mL.
5. The method as described in claim 4, characterized in that, The mass ratio of the three-dimensional honeycomb tubular carbon material to the volume of methanol in step 1) is 100:100, with mass in mg and volume in mL.
6. The method as described in claim 1, characterized in that, Step 2) The mass-to-volume ratio of the conjugated system compound with the two-dimensional cobalt tetracoordinate structure to methanol is 2-20 : 20-150, where the mass unit is mg and the volume unit is mL.
7. The method as described in claim 6, characterized in that, Step 2) The mass ratio of the conjugated system compound with the two-dimensional cobalt four-coordinate structure to methanol is 6:50, with mass in mg and volume in mL.
8. The method as described in claim 1, characterized in that, Step 3) The volume ratio of the two-dimensional cobalt four-coordinate structure conjugated system compound dispersion and the three-dimensional honeycomb structure tubular carbon material dispersion is 1:1-3.
9. The method as described in claim 8, characterized in that, Step 3) The volume ratio of the two-dimensional cobalt four-coordinate structure conjugated system compound dispersion and the three-dimensional honeycomb structure tubular carbon material dispersion is 1:
2.
10. The method as described in claim 1, characterized in that, In step 4), the drying temperature in the vacuum drying oven is 50-80℃, and the time is 4-24 h.
11. The method as described in claim 10, characterized in that, In step 4), the drying temperature in the vacuum drying oven is 60℃ and the time is 8 hours.
12. A composite structural material consisting of a two-dimensional cobalt four-coordinate conjugated system compound and a three-dimensional honeycomb tubular carbon material prepared by the method described in any one of claims 1 to 11.
13. The application of a composite structural material of a two-dimensional cobalt tetracoordinate conjugated system compound as described in claim 12 and a three-dimensional honeycomb tubular carbon material in the activated persulfate degradation of pollutants.
14. The application as described in claim 13, characterized in that, A composite structural material consisting of the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material was added to an aqueous solution of pollutants. After stirring, persulfate was added, and the resulting mixed solution was subjected to pollutant degradation under stirring.
15. The application as described in claim 14, characterized in that, The mass ratio of the composite structural material of the two-dimensional cobalt four-coordinate conjugated system compound and the three-dimensional honeycomb tubular carbon material to the mass of persulfate is 2~50 : 10-30.