A three-dimensional cobalt metal organic complex and a preparation method and application thereof

Abstract

This invention discloses a three-dimensional cobalt metal-organic complex, its preparation method, and its applications, belonging to the field of crystal materials technology. This invention uses 2,5-diketopiperazine-N,N'-diacetic acid and 4,4'-bipyridine as raw materials with cobalt ions to prepare a compound with the chemical formula [Co(DPDA)(4,4'-bpy)]. n A three-dimensional cobalt-organic metal complex. It has a six-connected three-dimensional network structure with dual-core [Co2(COO)2] structural units, and its topological symbol is {3 12 0.4 24 0.5 9 Furthermore, the aforementioned three-dimensional cobalt metal-organic complex can rapidly activate peroxymonosulfate to effectively degrade dyes. It can degrade methylene blue, malachite green, and crystal violet to over 95.0% within 5 minutes, without producing toxic byproducts during the degradation process, and exhibits good reusability. Additionally, the synthesis conditions of the three-dimensional cobalt metal-organic complex are mild, the steps are simple, and it possesses excellent structural stability, good thermal stability, and antiferromagnetism at high temperatures.

Description

Technical Field

[0001] This invention belongs to the field of crystal materials technology, specifically relating to a three-dimensional cobalt metal organic complex, its preparation method, and its application. Background Technology

[0002] Currently, water pollution treatment methods mainly include biological treatment, physical adsorption, chemical oxidation, and photocatalytic degradation. Most traditional methods have been found to have low dye removal efficiency and high operating costs. In addition, toxic byproducts are generated at the end of the conventional treatment process.

[0003] Metal-organic frameworks (MOFs) are novel porous materials assembled through coordination bonds using metal ions or metal clusters as nodes or secondary structural units and multifunctional organic ligands as connectors. These materials possess characteristics such as high porosity, high specific surface area, and tunable structure. However, most publicly available MOFs that degrade dyes suffer from drawbacks such as poor stability, slow degradation rates, secondary pollution, and low recyclability, which hinder their application to some extent. Therefore, designing and synthesizing MOFs with stable structures and degradation capabilities for various dyes is of great significance for dye wastewater treatment and environmental protection. Summary of the Invention

[0004] To address the shortcomings of the prior art, this invention provides a three-dimensional cobalt metal-organic complex, its preparation method, and its applications. The three-dimensional cobalt metal-organic complex of this invention can rapidly activate peroxymonosulfate to generate free radicals, rapidly degrade organic dyes in less than 5 minutes, and exhibits a very low leaching rate of Co ions. It also demonstrates good stability and reproducibility, making it suitable for practical applications.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A three-dimensional cobalt-organic complex with the chemical formula [Co(DPDA)(4,4'-bpy)] n DPDA 2- The ligand represents the divalent anion of 2,5-dikepiperazine-N,N'-diacetic acid after losing two protons; the 4,4'-bpy ligand represents the electrically neutral 4,4'-bipyridine ligand; Co represents the divalent cobalt ion; and n represents a non-zero natural number.

[0007] As a preferred embodiment of the present invention, the crystal structure of the three-dimensional cobalt metal-organic complex belongs to the monoclinic crystal system, space group C2; the unit cell parameters are: α=90°, β=100.177(3)°, γ=90°.

[0008] In a preferred embodiment of the present invention, the central Co(II) ion of the three-dimensional cobalt organometallic complex adopts a six-coordinate configuration, forming four O atoms from four different DPDA ligands, with the apex occupied by two 4,4'-bpy N atoms; the four O atoms in the complex are in the same plane, and the bond angle of N1A-Co2-N2 is 180°, forming a tetragonal bipyramidal structure; the bond lengths of Co-N and Co-O at the center of the Co(II) ion are respectively...

[0009] In a preferred embodiment of the present invention, the cobalt metal-organic complex is a three-dimensional network structure, which can be simplified to a six-connected topology of a dual-core [Co2(COO)2] structural unit, with the topological symbol {3}. 12 0.4 24 0.5 9}

[0010] This invention also claims a method for preparing the three-dimensional cobalt metal-organic complex, comprising the following steps: dissolving cobalt salt and 4,4'-bpy in a mixed solution of H2O and methanol to obtain solution A; dissolving H2DPDA crystals in NaOH solution to obtain solution B; mixing solution A and solution B uniformly; and then performing a hydrothermal reaction to obtain the three-dimensional cobalt metal-organic complex.

[0011] As a preferred embodiment of the present invention, the preparation method of the H2DPDA crystal includes the following steps: mixing iminodiacetic acid, phosphoric acid and water evenly and then carrying out a hydrothermal reaction, and cooling to room temperature to obtain H2DPDA crystal;

[0012] In a preferred embodiment of the present invention, the hydrothermal reaction of the iminodiacetic acid, phosphoric acid and water after uniform mixing is carried out at a temperature of 170°C for 12 hours.

[0013] In a preferred embodiment of the present invention, the molar ratio of the cobalt salt, H2DPDA and 4,4'-bpy is 1:(0.5-1.5):(1-3).

[0014] In a preferred embodiment of the present invention, the volume ratio of H2O to methanol is (9-12):2.

[0015] In a preferred embodiment of the present invention, the molar ratio of H2DPDA to NaOH is 1:(1 to 2.2).

[0016] In a preferred embodiment of the present invention, the hydrothermal reaction of the mixture of solution A and solution B is carried out at a temperature of 100°C for a time of 72 hours.

[0017] In a preferred embodiment of the present invention, the cobalt source is one of cobalt acetate, cobalt sulfate, and cobalt nitrate.

[0018] This invention also claims protection for the application of the three-dimensional cobalt metal-organic complex, including the following steps:

[0019] The described three-dimensional cobalt-organic metal complex effectively degrades three dyes: methylene blue (MB), malachite green (MG), and crystal violet (CV). The amount of the three-dimensional cobalt-organic metal complex was 10 mg, the amount of peroxymonosulfate was 15 mg, and the concentrations of methylene blue (MB), malachite green (MG), and crystal violet (CV) were all 40 mg / L. All three dyes exhibited good degradation ability under a xenon lamp light source. The degradation ability of the three-dimensional cobalt-organic metal complex on methylene blue (MB), malachite green (MG), and crystal violet (CV) was monitored by UV-Vis. Experimental data showed that the degradation rate of methylene blue (MB) reached over 99% within 5 minutes, while the degradation rates of malachite green (MG) and crystal violet (CV) were over 99% and 96%, respectively.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] (1) The three-dimensional cobalt organometallic complex of the present invention is prepared using 2,5-dikepiperazine-N,N'-diacetic acid and 4,4'-bipyridine as dual ligands and Co as the metal ion. Compared with ordinary metal-organic framework materials, it has more active sites and structural stability, and the prepared three-dimensional cobalt organometallic complex has excellent degradation performance; it can effectively activate peroxymonosulfate to degrade methylene blue (MB), malachite green (MG), and crystal violet (CV) dyes. Experiments show that the degradation rates of methylene blue (MB), malachite green (MG), and crystal violet (CV) within 5 min are 99.82%, 99.70%, and 96.68%, respectively. In addition, the three-dimensional cobalt organometallic complex of the present invention has good stability and recyclability. It can maintain the main structural framework without collapsing at 300°C. After 5 cycles, the catalyst can still achieve a degradation rate of over 90%.

[0022] (2) The preparation method of the three-dimensional cobalt metal-organic complex of the present invention is mild, simple, highly operable, low in energy consumption, and has a high yield during synthesis. The metal-organic framework material has excellent economic efficiency and feasibility. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the crystal structure of the three-dimensional cobalt metal organic complex prepared in Example 1 of the present invention.

[0024] Figure 2 This is a three-dimensional stacked structure diagram of the three-dimensional cobalt metal organic complex prepared in Example 1 of the present invention.

[0025] Figure 3 This is a topological diagram of the three-dimensional crystal structure of the three-dimensional cobalt metal-organic complex prepared in Example 1 of this invention.

[0026] Figure 4 This is the infrared spectrum of the three-dimensional cobalt metal-organic complex prepared in Example 1.

[0027] Figure 5 These are experimental and simulated powder diffraction patterns of the three-dimensional cobalt metal organic complex prepared in Example 1.

[0028] Figure 6 This is a thermogravimetric curve of the three-dimensional cobalt metal organic complex prepared in Example 1.

[0029] Figure 7 This is a temperature-dependent magnetic susceptibility curve of the three-dimensional cobalt metal-organic complex prepared in Example 1.

[0030] Figure 8 The three-dimensional cobalt metal organic complex prepared in Example 1 catalyzes the degradation of methylene blue, malachite green, and crystal violet by potassium persulfate.

[0031] Figure 9 The degradation efficiency of methylene blue by potassium persulfate at different pH values ​​is catalyzed by the three-dimensional cobalt metal-organic complex prepared in Example 1.

[0032] Figure 10 This is the cyclic result of potassium persulfate degradation of methylene blue catalyzed by the three-dimensional cobalt metal-organic complex prepared in Example 1.

[0033] Figure 11 The images show the XRD patterns of the three-dimensional cobalt metal-organic complex prepared in Example 1 before and after the reaction of potassium persulfate to degrade methylene blue. Detailed Implementation

[0034] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0035] Example 1

[0036] A method for preparing a three-dimensional cobalt metal-organic complex includes the following steps:

[0037] (1) Mix 9.0g iminodiacetic acid, 6.9ml phosphoric acid and 540ml water evenly in polytetrafluoroethylene and react at a high temperature of 170℃ for 12 hours. Cool to room temperature to obtain H2DPDA crystals.

[0038] (2) Dissolve 0.4 mmol Co(NO3)2·6H2O and 0.4 mmol 4,4'-bpy in a mixed solution of 4 ml H2O and methanol (volume ratio 9:2); dissolve 0.2 mmol H2DPDA crystals in 2 ml of 0.2 mol / L NaOH solution. Mix the two solutions thoroughly, then transfer them to polytetrafluoroethylene (PTFE) and crystallize at 100 °C for 72 hours. Then, crystallize at 5 °C·h. -1 The rate was reduced to room temperature to obtain three-dimensional cobalt metal-organic complexes.

[0039] The study found that when the molar ratio of Co(NO3)2·6H2O, H2DPDA and 4,4'-bpy was 1:0.5:1, the resulting three-dimensional cobalt organometallic complex had the most complete crystallinity, the largest single crystal volume, and relatively uniform crystal particles, with a yield of 78.62%.

[0040] Example 2

[0041] A method for preparing a three-dimensional cobalt metal-organic complex includes the following steps:

[0042] (1) Mix 9.0g iminodiacetic acid, 6.9ml phosphoric acid and 540ml water evenly in polytetrafluoroethylene and react at a high temperature of 170℃ for 12 hours. Cool to room temperature to obtain H2DPDA crystals.

[0043] (2) Dissolve 0.4 mmol Co(NO3)2·6H2O and 1.2 mmol 4,4'-bpy in a mixed solution of 4 ml H2O and methanol (volume ratio 9:2); dissolve 0.6 mmol H2DPDA crystals in 2 ml of 0.3 mol / L NaOH solution. Mix the two solutions thoroughly, then transfer them to polytetrafluoroethylene and crystallize at 100 °C for 72 hours, then at 5 °C·h. -1 The rate was reduced to room temperature to obtain three-dimensional cobalt metal-organic complexes.

[0044] The study found that when the molar ratio of Co(NO3)2·6H2O, H2DPDA and 4,4'-bpy was 1:1.5:3, the resulting three-dimensional cobalt organometallic complex crystals had relatively complete crystallinity, with medium-sized individual crystals and relatively irregular crystal particles, and the yield of the three-dimensional cobalt organometallic complex was 68.57%.

[0045] Example 3

[0046] A method for preparing a three-dimensional cobalt metal-organic complex includes the following steps:

[0047] (1) Mix 9.0g iminodiacetic acid, 6.9ml phosphoric acid and 540ml water evenly in polytetrafluoroethylene and react at a high temperature of 170℃ for 12 hours. Cool to room temperature to obtain H2DPDA crystals.

[0048] (2) Dissolve 0.4 mmol Co(NO3)2·6H2O and 0.4 mmol 4,4'-bpy in a mixed solution of 4 ml H2O and methanol (volume ratio 12:2); dissolve 0.4 mmol H2DPDA crystals in 2 ml of 0.44 mol / L NaOH solution. Mix the two solutions thoroughly, then transfer them to polytetrafluoroethylene (PTFE) and crystallize at 100 °C for 72 hours. Then, crystallize at 5 °C·h. -1 The rate was reduced to room temperature to obtain three-dimensional cobalt metal-organic complexes.

[0049] The study found that when the molar ratio of Co(NO3)2·6H2O, H2DPDA and 4,4'-bpy was 1:1:1, the resulting three-dimensional cobalt organometallic complex crystals had relatively complete crystallinity, small individual crystal volume but relatively uniform crystal particles, and the yield of the three-dimensional cobalt organometallic complex was 65.91%.

[0050] Example 4

[0051] The only difference between the preparation method of the three-dimensional cobalt metal organic complex in this embodiment and that in Example 1 is that Co(NO3)2·6H2O in step (2) is replaced with an equimolar amount of Co(OAc)2·4H2O.

[0052] Example 5

[0053] The only difference between the preparation method of the three-dimensional cobalt metal organic complex in this embodiment and that in Example 1 is that Co(NO3)2·6H2O in step (2) is replaced with an equimolar amount of CoSO4·7H2O.

[0054] A comparison of Examples 1 and 4-5 shows that when Co(NO3)2·6H2O is selected as the cobalt source, the resulting three-dimensional cobalt metal organo-complex crystals have the most complete crystallinity, and the volume and particle size of individual crystals are relatively uniform.

[0055] Example 1

[0056] Single-crystal X-ray intensity data were obtained using graphite monochromatic Mo Kα radiation. The data were acquired at 296(2) K using a Bruker SMARTAPEX II diffractometer. The structure was solved and the space group determined using the direct method with the ShelXS-97 structure solver (Sheldrick, 2008), and then refined on F2 using the full matrix least squares minimization method with the ShelXL-97 version (Sheldrick, 2008). All non-hydrogen atoms were refined using anisotropic methods, and the positions of hydrogen atoms were obtained through geometric calculations and refined using a riding model. Some parameters of the crystal diffraction data collection and structure refinement of the three-dimensional cobalt organometallic complex prepared in Example 1 are shown in Table 1.

[0057] Table 1

[0058]

[0059]

[0060] The three-dimensional cobalt metal-organic complexes prepared in Examples 1-5 have the same structure, such as... Figure 1 Its central Co(II) ion adopts a six-coordinate system, interacting with four different DPDA groups. 2- The ligand consists of four O atoms, while the apex position is occupied by two N atoms in a 4,4'-bpy configuration. The four O atoms in the complex are almost in the same plane, and the bond angle between N1A-Co2-N2 is 180°, forming a tetragonal bipyramidal structure. The bond lengths of Co-N and Co-O at the center of Co(II) range from [missing information]. and

[0061] like Figure 2 As shown, in the three-dimensional cobalt metal-organic complexes prepared in Examples 1-5 of this invention, two adjacent Co(II) ions are bonded by two DPDA bonds. 2- The terminal carboxyl group of the ligand bridges the structure, forming a [Co2(COO)2] binuclear unit. Here, each DPDA... 2- All ligands were completely deprotonated and in μ2-η 2 :η 2 A dual-bridged mode connects two adjacent [Co2(COO)2] binuclear structural units. Simultaneously, the 4,4'-bpy ligand employs μ2-η... 1 :η 1 The coordination mode connects adjacent [Co2(COO)2] binucleate structural units into an infinitely extending one-dimensional chain. Therefore, each binucleate [Co2(COO)2] extends infinitely into a three-dimensional network framework through six bridging ligands. Each [Co2(COO)2] binucleate cluster is considered a six-connected node, as shown below. Figure 3The general structure can be simplified to a three-dimensional, six-connected topological network, with the topological symbol {3}. 12 0.4 24 0.5 9}

[0062] The three-dimensional cobalt-based organometallic complexes prepared in Examples 1-5 have the same structure; only the relevant detection results of the three-dimensional cobalt-based organometallic complex prepared in Example 1 will be shown subsequently. Figure 4 As shown, Example 1 was performed at 3511 cm. -1 A broad and strong infrared peak is observed at 2944 cm⁻¹, which coincides with the OH bond of the H₂O molecule. -1 The weak absorption band at approximately 1651 cm⁻¹ is due to the stretching vibration of the aromatic CH group. -1 The structure exhibits both symmetric and asymmetric stretching vibrations at C=O, and at 1308 cm⁻¹ -1 Characteristic CN stretching vibrations were observed. Meanwhile, the C=C stretching vibrations of the aromatic ring skeleton were located at 1497 cm⁻¹. -1 The absorption peaks of the aromatic ring CH bond are at 400 and 800 cm⁻¹. -1 The above demonstrates that the complex of Example 1 has been successfully prepared. Figure 5 As shown, comparing the XRD curve of Example 1 with the curve obtained from simulated crystal data, it can be seen that the complex prepared in Example 1 is a pure phase. Figure 6 As shown, the cobalt metal organic complex prepared in Example 1 begins to collapse its crystal structure after 300°C, exhibiting good thermal stability.

[0063] Example 2

[0064] The three-dimensional cobalt metal-organic complex obtained in Example 1 was subjected to variable-temperature magnetic susceptibility testing under an applied DC magnetic field of 1000 Oe.

[0065] The temperature-dependent magnetization curves of the prepared three-dimensional cobalt-based organometallic complexes are as follows: Figure 7 As shown, the temperature-dependent magnetic susceptibility χ of this complex at 300K can be observed. M The T value is 3.00 cm. 3 ·K·mol -1 3.75 cm below two independent Co(II) atoms 3 ·K·mol -1 This may be due to the stronger spin-orbit coupling in the octahedral environment. As the temperature decreases, χ... M The T value decreased slowly, reaching 2.49 cm at 32K. 3 ·K·mol -1 Subsequently, χ M The T-value suddenly increases, reaching a maximum of 3.84 cm at 4K. 3·K·mol -1 , χ M The sharp increase in T value can be attributed to interchain ferromagnetic interactions between adjacent cobalt ion centers, which decrease to 2.51 cm at 2 K. 3 ·K·mol -1 This is attributed to antiferromagnetic interactions and spin-orbit coupling, indicating that the complex exhibits antiferromagnetism at high temperatures.

[0066] Example 3

[0067] Test samples: Three-dimensional cobalt metal organo-complexes prepared in Examples 1, 2, 3, 4 or 5.

[0068] Test method: Weigh 10 mg of test sample and add it to 50 ml of dye aqueous solution (40 mg / L). Stir in the dark for 30 min to allow the complex surface to reach adsorption-desorption equilibrium. Then add 15 mg of potassium persulfate and introduce a 10 W xenon lamp light source. The temperature is room temperature and the pH is 7.

[0069] like Figure 8 As shown, the three-dimensional cobalt metal organic complex obtained in Example 1 showed a degradation rate of up to 99.82% for methylene blue, 99.70% for malachite green, and 96.68% for crystal violet within 5 minutes after the addition of potassium persulfate.

[0070] The three-dimensional cobalt metal-organic complexes obtained in Examples 2-5 have the same structure as those in Example 1, and their effects on the degradation of methylene blue, malachite green and crystal violet dyes are similar to those in Example 1.

[0071] The results show that the three-dimensional cobalt-based organometallic complex of the present invention has a high degradation rate for the three dyes and can degrade a variety of dyes. The three-dimensional cobalt-based organometallic complex of the present invention is a highly efficient catalyst for dye degradation.

[0072] Example of effect 4

[0073] Test samples: Three-dimensional cobalt metal organo-complexes prepared in Examples 1, 2, 3, 4 or 5.

[0074] Test method: Weigh 10 mg of the test sample and add it to 50 ml of methylene blue aqueous solution (40 mg / L). Stir in the dark for 30 min to allow the complex surface to reach adsorption-desorption equilibrium. Then add 15 mg of potassium persulfate and introduce a 10 W xenon lamp light source. The pH range for the degradation of methylene blue dye on the three-dimensional cobalt organometallic complex is tested at room temperature and pH values ​​of 3, 5, 7, 9, and 11. Figure 9As shown, the complex prepared in Example 1 exhibits a strong ability to catalyze the degradation of potassium persulfate within the pH range of 3-11, which means that it can be practically applied under the same environmental conditions.

[0075] The three-dimensional cobalt metal-organic complexes obtained in Examples 2-5 have the same structure as those in Example 1, and their degradation of methylene blue dye at different pH values ​​is similar to that in Example 1.

[0076] Example 5

[0077] Test samples: Three-dimensional cobalt metal organo-complexes prepared in Examples 1, 2, 3, 4 or 5.

[0078] Test method: Weigh 10 mg of the test sample and add it to 50 ml of methylene blue aqueous solution (40 mg / L). Stir in the dark for 30 min to allow the complex surface to reach adsorption-desorption equilibrium. Then add 15 mg of potassium persulfate and introduce a 10 W xenon lamp light source. The temperature is room temperature and pH is 7. Perform a reusability test on the methylene blue dye degradation of the three-dimensional cobalt organometallic complex. Figure 10 As shown, after five cycles of catalytic degradation of potassium persulfate by the complex prepared in Example 1, the degradation efficiency of methylene blue remained above 90%, indicating that the complex has stable catalytic activity and can be reused.

[0079] The three-dimensional cobalt metal-organic complexes obtained in Examples 2-5 have the same structure as those in Example 1, and their performance in the recovery experiment of degrading methylene blue dye is similar to that in Example 1.

[0080] Example 6

[0081] Does the three-dimensional cobalt-based organometallic complex leach cobalt ions during dye degradation? Figure 11 As shown, comparing the XRD curves of methylene blue dye before and after degradation in Example 1, it can be seen that Co ions can rapidly activate PMS to generate free radicals that degrade the dye. However, excessive Co ion overflow will pollute the environment. Compared with the newly prepared complex, the experimental data obtained by Co-MOFs@methylene blue material have some differences in peak intensity, but the main peaks still exist and the framework has not collapsed. This indicates that Example 1 does not generate too much toxic byproduct Co ions during the degradation process.

[0082] In summary, the three-dimensional cobalt-based organometallic complex of the present invention exhibits excellent performance in the field of dye degradation, showing high degradation efficiency for MB, MG, and CV dyes. It is a highly efficient catalyst and is expected to be widely used in various environments to remove organic pollutants.

[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A three-dimensional cobalt metal-organic complex, characterized in that, [Co(DPDA)(4,4'-bpy)] n , DPDA 2- The ligand represents a dianion of 2,5-diketopiperazine-N,N'-dipropionic acid from which two protons are lost, the 4,4'-bpy ligand represents an electrically neutral 4,4'-bipyridine ligand, Co represents a positive divalent cobalt ion, and n represents a natural number other than zero. The crystal structure of the three-dimensional cobalt metal-organic complex belongs to the monoclinic crystal system, space group C2; the cell parameters are: a=17.5291(19)Å, b=11.4495(11)Å, c=9.6006(9)Å; α=90°, β=100.177(3)°, γ=90°; The cobalt metal organic complex is a three-dimensional network structure, a six-connected topology structure of binuclear [Co2(COO)2] structural unit, and the topological symbol is {3 12 .4 24 .5 9} 2. The method for preparing the three-dimensional cobalt metal organo-complex according to claim 1, characterized in that, The process includes the following steps: dissolving a cobalt source and 4,4'-bpy in a mixed solution of H2O and methanol to obtain solution A; dissolving H2DPDA crystals in NaOH solution to obtain solution B; mixing solutions A and B thoroughly; and then reacting them hydrothermally to obtain a three-dimensional cobalt metal organo-complex.

3. The method for preparing the three-dimensional cobalt metal organo-complex as described in claim 2, characterized in that, The volume ratio of H2O to methanol is (9~12):

2.

4. The method for preparing the three-dimensional cobalt metal-organic complex as described in claim 2, characterized in that, The molar ratio of H2DPDA to NaOH is 1:(1~2.2).

5. The method for preparing the three-dimensional cobalt metal-organic complex as described in claim 2, characterized in that, The molar ratio of the cobalt source, H2DPDA and 4,4'-bpy is 1:(0.5~1.5):(1~3).

6. The method for preparing the three-dimensional cobalt metal-organic complex as described in claim 2, characterized in that, The hydrothermal reaction was carried out at a temperature of 100°C for 72 hours.

7. The method for preparing the three-dimensional cobalt metal organo-complex as described in claim 2, characterized in that, The cobalt source is one of cobalt acetate, cobalt sulfate, or cobalt nitrate.

8. The application of the three-dimensional cobalt metal organic complex of claim 1 in the catalytic degradation of organic pollutants by activated peroxymonosulfate.

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