Co-MOF material based on 1-aminobenzene-3, 4, 5-tricarboxylic acid, preparation method and application

Abstract

The invention discloses a Co-MOF (Metal Organic Framework) material based on 1-aminobenzene-3, 4, 5-tricarboxylic acid as well as a preparation method and application of the Co-MOF material. The invention discloses a preparation method of cobalt acetate. The preparation method comprises the following steps: sealing a mixture of 4, 4 '-azobipyridine, acetonitrile and water in a 10mL small glass bottle, carrying out a hydrothermal reaction, adding a mixture of 1-aminobenzene-3, 4, 5-tricarboxylic acid and water, stirring, adjusting the pH value to 9, continuing to carry out a sealed reaction for 24 hours, cooling to room temperature, washing, and drying to obtain the high-crystallinity Co-MOF material. The preparation method is simple and feasible. The Co-MOF material has good friction power generation performance and stability, and when the Co-MOF material is applied to a vertical contact separation type friction nanometer generator and water pollution treatment, the device can efficiently degrade 98.8% of methylene blue within 90 minutes under the working condition of 5Hz.

Description

Technical Field

[0001] The present invention belongs to the technical field of triboelectric materials, and specifically relates to a Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid, a preparation method, and a triboelectric nanogenerator design thereof, and their application in water pollution treatment. Background Art

[0002] With the advancement of industry and the rapid development of cities, energy shortages and water pollution have quietly become two pressing challenges facing humanity. However, the complexity of pollutants and the difficulty in treating refractory pollutants make wastewater treatment a highly energy-intensive process. Consequently, there is an urgent need to develop an economical, environmentally friendly, and efficient wastewater treatment solution. However, triboelectric nanogenerators (TNGs) offer significant advantages, such as high energy conversion efficiency, simple structure, and high flexibility, making them ideal energy harvesters and energy supply devices in various environments. Therefore, utilizing TNGs to harvest energy from the environment and thereby degrade organic pollutants in water is an ideal approach.

[0003] In the research on friction nanogenerators, their high performance output is closely related to the surface charge density of the friction dielectric material and its dynamic behavior. Increasing the surface charge density of the friction layer by selecting suitable friction power generation materials is the most effective way to fundamentally improve the performance of friction nanogenerators. Summary of the Invention

[0004] In response to the problems existing in the prior art, the present invention provides a Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid, its preparation method and application. The material is a high-efficiency filler for improving the output performance of triboelectric nanogenerators. The present invention uses 4,4'-azobipyridine and 1-aminobenzene-3,4,5-tricarboxylic acid as organic ligands and constructs a crystalline MOF material with a three-dimensional porous structure through step-by-step assembly with cobalt ions. 1.5 (L)(4,4'-azobpy)(H2O)]·6.5H2O} n (Co-MOF), a material with excellent photoluminescence and triboelectric properties. Furthermore, using this material as an electrode material for a vertical contact-separation triboelectric nanogenerator demonstrates excellent output performance and cycling stability, providing a strong foundation for the construction of a self-powered wastewater treatment system.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid, wherein the chemical formula of the Co-MOF material is {[Co 1.5(L)(4,4'-azobpy)(H2O)]·6.5H2O} n , n is a non-zero natural number, and L is 1-aminobenzene-3,4,5-tricarboxylic acid.

[0007] Furthermore, the Co-MOF material is a crystalline material, belonging to the monoclinic system, space group C2 / c, and the unit cell parameters are α=90°,β=124.31(3)°,γ=90°,its minimum structural unit consists of 1.5 Co 2+ , 1 L 3- , 1 4,4'-azopyridine, a coordinated water molecule and 7 guest water molecules.

[0008] The present invention also provides a method for preparing the Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid, comprising the following steps: sealing a mixture of cobalt acetate, 4,4'-azobipyridine, acetonitrile and water in a 10 mL glass vial, fully shaking it in an ultrasonic cleaner until it is completely dissolved, and then placing it in an oven for hydrothermal reaction A. After the reaction is completed, the glass vial is taken out, and a mixture of 1-aminobenzene-3,4,5-tricarboxylic acid and water is added, stirred and adjusted to pH = 9, and the vial is continued to be sealed in the oven for hydrothermal reaction B, followed by slow cooling to room temperature to obtain purple block crystals, washing with mother liquor, and drying to obtain a Co-MOF-based triboelectric material.

[0009] Furthermore, the molar ratio of the cobalt acetate, 4,4'-azobipyridine and 1-aminobenzene-3,4,5-tricarboxylic acid is 2:1:1.

[0010] Furthermore, the volume ratio of acetonitrile to water is 1:2. Based on 0.1 mmol of cobalt acetate, 2 mL of acetonitrile and 4 mL of water are required.

[0011] Furthermore, the temperature of the hydrothermal reaction A is 100° C., and the time of the hydrothermal reaction A is 24 hours.

[0012] Furthermore, in the mixture of 1-aminobenzene-3,4,5-tricarboxylic acid and water, the concentration of 1-aminobenzene-3,4,5-tricarboxylic acid is 0.05 mol / L, and the pH is adjusted to 9 using 2M sodium hydroxide solution.

[0013] Furthermore, the temperature of the hydrothermal reaction B is 100° C., the time of the hydrothermal reaction B is 24 hours, and the cooling rate when cooling to room temperature is 15° C. / h.

[0014] The present invention also provides the application of Co-MOF materials based on 1-aminobenzene-3,4,5-tricarboxylic acid in the construction of a vertical contact separation friction nanogenerator: Co-MOF is used to construct a friction nanogenerator Co-MOF-TENG. Using polyvinylidene fluoride material as a counter electrode, the current, charge density, and electric power density of Co-MOF-TENG were tested. The results show that Co-MOF can be used as a friction nanogenerator to effectively utilize mechanical energy. Specifically: Co-MOF material is used as a friction nanogenerator to construct a friction nanogenerator Co-MOF-TENG, copper sheet and Kapton film are used as the conductive layer and charge storage layer respectively, Co-MOF and polyvinylidene fluoride are used as the friction layer. After 50,000 cycles, the current can stably reach 90.59μA, the open circuit voltage can reach 469.12V, and the charge density can reach 134.6μC·m -2 , the power density reaches 3328.49mW / m 2 above.

[0015] The present invention also provides the application of the Co-MOF-TENG constructed with the Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid in the degradation of organic pollutants: under the drive of the Co-MOF-TENG device, a two-electrode system is used to electrochemically degrade organic pollutants, wherein the straw biochar material and the platinum sheet are the anode and cathode electrodes, the electrode spacing is 1.5 cm, and a 0.07M sodium sulfate solution is used as the initial simulation treatment solution. The output signal of the Co-MOF-TENG is rectified, and two copper wires are respectively connected to the rectifier to integrate the alternating current into direct current to promote its coupling with the electrochemical degradation system. When the friction nanogenerator Co-MOF-TENG device operates at 5Hz, the device achieves 98.8% efficient degradation of methylene blue within 90 minutes.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. The Co-MOF of the present invention is prepared by a common hydrothermal process. The preparation method is simple and easy, the ligand is simple and easy to synthesize, the yield is high, and batch production is easy, which reduces costs. It provides a new choice for optoelectronic materials and expands the application value of crystalline MOF materials.

[0018] 2. The triboelectric material of the present invention has good stability, maintains a good crystalline state below 300 degrees, and maintains a stable output state after 50,000 cycles of triboelectric power generation test, laying the foundation for commercial application.

[0019] 3. The self-powered sewage treatment system constructed by the present invention can achieve a degradation rate of 98.8% of organic dyes within 90 minutes, realizing a green and environmentally friendly sewage purification method. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is the molecular formula of 1-aminobenzene-3,4,5-tricarboxylic acid ligand used in material preparation.

[0021] Figure 2 It is the molecular formula of the azopyridine ligand used in material preparation.

[0022] Figure 3 This is the structure diagram of the crystalline material Co-MOF in Example 1.

[0023] Figure 4 This is a crystal photograph of the crystalline material Co-MOF in Example 1.

[0024] Figure 5 This is the Fourier infrared spectrum of the crystalline material Co-MOF in Example 1.

[0025] Figure 6 This is the X-ray powder diffraction pattern of the crystalline material Co-MOF in Example 1.

[0026] Figure 7 This is a scanning electron microscope image of the crystalline material Co-MOF in Example 1.

[0027] Figure 8 This is the thermogravimetric diagram of the crystalline material Co-MOF in Example 1.

[0028] Figure 9 This is the ultraviolet-visible absorption spectrum of the crystalline material Co-MOF in Example 1.

[0029] Figure 10 This is the X-ray photoelectron spectrum of the crystalline material Co-MOF in Example 1.

[0030] Figure 11 This is the N2 adsorption-desorption curve of the crystalline material Co-MOF in Example 1.

[0031] Figure 12 Short-circuit current diagram of Co-MOF-TENG under 5Hz operation.

[0032] Figure 13 Charge density diagram of Co-MOF-TENG under 5Hz operation.

[0033] Figure 14 Open-circuit voltage diagram of Co-MOF-TENG under 5Hz operation.

[0034] Figure 15 Co-MOF-TENG electric power density test diagram under 5Hz working condition.

[0035] Figure 16Short-circuit current cycling stability of Co-MOF-TENG under 5Hz operation.

[0036] Figure 17 Image of Cd-MOF-TENG lighting up LED lamp at 5Hz operation.

[0037] Figure 18 Schematic diagram of electrochemical degradation of organic pollutants using a two-electrode system driven by the Co-MOF-TENG device.

[0038] Figure 19 Comparison of MB degradation rate with and without Co-MOF-TENG under 5HZ working conditions within 90 min. DETAILED DESCRIPTION

[0039] The above contents of the present invention are further described in detail below through examples, but this should not be understood as limiting the scope of the above subject matter of the present invention to the following examples. All technologies implemented based on the above contents of the present invention fall within the scope of the present invention.

[0040] Example 1

[0041] The preparation method of the Co-MOF triboelectric material based on 1-aminobenzene-3,4,5-tricarboxylic acid in this embodiment is as follows:

[0042] A mixture of cobalt acetate (Co(CH3COO)2.4H2O) (0.025 g, 0.1 mmol), 4,4'-azobipyridine (4,4'-azobpy) (0.0092 g, 0.05 mmol), acetonitrile (2 mL), and H2O (4 mL) was sealed in a 10 mL glass vial and thoroughly shaken in an ultrasonic cleaner until completely dissolved. The mixture was then placed in a 100°C oven to react for 4 hours. A mixture of 1-aminobenzene-3,4,5-tricarboxylic acid (C9H7NO6) (0.0112 g, 0.05 mmol) and water (1 mL) was stirred and adjusted to pH = 9 with 2M sodium hydroxide solution. The mixture was sealed and reacted in a 100°C oven for 24 hours. The temperature was cooled to room temperature at a rate of 15°C / h to obtain purple block crystals, which were washed with the mother liquor and dried to obtain the Co-MOF triboelectric material (Co-CP) based on 1-aminobenzene-3,4,5-tricarboxylic acid.

[0043] The crystallographic parameters of Co-MOF are detailed in the table below.

[0044]

[0045] Test Example 1

[0046] Fourier transform infrared spectroscopy analysis of the Co-MOF material prepared in Example 1

[0047] The Co-MOF material in Example 1 was placed in a mortar and ground for 0.5 h to obtain a uniform powder, which was then placed in a mold together with pure KBr and pressed into a transparent sheet on a hydraulic press. The powder was then tested using a Fourier transform infrared spectrometer, and the fluorescence emission spectrum was obtained by selecting a wavelength range of 400-4000 nm. Figure 5 As shown. By Fourier infrared spectroscopy analysis, at 3200cm -1 and 800cm -1 Characteristic peaks appeared at 1706.6 cm-1, corresponding to the NH stretching vibration absorption and out-of-plane bending vibration absorption. -1 There is an obvious absorption peak at the center, indicating the existence of a carbon-oxygen bond. The ligands used in the synthetic material also contain carboxyl groups. Comprehensive infrared spectral data analysis further proves the successful synthesis of Co-MOF triboelectric material.

[0048] Test Example 2

[0049] X-ray powder diffraction analysis of the Co-MOF material in Example 1

[0050] The crystalline material Co-MOF was crushed and ground in a mortar for 0.5 hours to obtain a uniform powder. The powder X-ray diffraction pattern was obtained by using a PANalytical X'Pert PRO single crystal powder diffractometer and Cu-Kα ray radiation for 5 minutes. Figure 6 As shown, the peak position of the powder X-ray diffraction pattern obtained by the test is consistent with the theoretical pattern, which shows that the phase purity of the Co-MOF obtained in Example 1 is very high and can maintain a good crystalline state.

[0051] Test Example 3

[0052] Scanning electron microscopy analysis of Co-MOF materials in Example 1

[0053] Take a small amount of dried crystalline material Co-MOF, attach the sample to the conductive glue using the gold spraying method, and transfer it to the Zeiss scanning electron microscope. The image taken is as follows Figure 7 As shown, the image shows a regular appearance, approximately 10 microns in size, with a smooth, clean surface and no cracks. The elemental mapping image shows that the elements C, Co, N, and O are evenly distributed throughout the crystal material, which significantly improves the results obtained in subsequent tests.

[0054] Test Example 4

[0055] Thermogravimetric analysis of Co-MOF materials in Example 1

[0056] The dried Co-MOF material was placed in a Netzsch STA 449C thermal analyzer, air was introduced, and thermogravimetric analysis was performed at a heating rate of 10 °C min. Figure 8 As shown, Co-MOF can remain stable within 300°C, which indicates that the Co-MOF obtained in Example 1 has a wide temperature application range.

[0057] Test Example 5

[0058] Solid UV diffuse reflectance spectroscopy analysis of the Co-MOF material in Example 1

[0059] The dried Co-MOF material was placed in a mortar and ground for 0.5 h to obtain a uniform powder. The powder was then tested using a Lambda-950 UV-visible spectrophotometer, selecting a wavelength of 250-800 nm to obtain a UV-visible spectrum. Figure 9 As shown, Co-MOF has a strong absorption peak at 336 nm, which indicates that the Co-MOF obtained in Example 1 has a typical ultraviolet absorption characteristic peak of cadmium coordination polymer.

[0060] Test Example 6

[0061] X-ray photoelectron spectroscopy analysis of the Co-MOF material in Example 1

[0062] The Co-MOF material in Example 1 was placed in a mortar and ground for 0.5 h to obtain a uniform powder, which was then pressed into a thin sheet and coated on the conductive adhesive. The X-ray photoelectron spectrum (XPS) was measured using a Thermo Scientific K-Alpha X-ray photoelectron spectrometer. The X-ray photoelectron spectrum analysis image was obtained, as shown in FIG. Figure 10 As shown. Typical Co 2+ Characteristic ion peaks.

[0063] Test Example 7: N2 adsorption-desorption analysis of Co-MOF materials in Example 1

[0064] The Co-MOF material in Example 1 was placed in a mortar and ground for 0.5 h to obtain a uniform powder. The N2 adsorption-desorption analysis image was obtained using a Bayer fully automatic specific surface and pore analyzer at 273 K. Figure 11 As shown, it exhibits weak N2 adsorption performance.

[0065] Example 2

[0066] Application of the Co-MOF material prepared in Example 1 in the preparation of triboelectric nanogenerator Co-MOF-TENG

[0067] The Co-MOF material crystals prepared in Example 1 were used to construct a triboelectric nanogenerator (Co-MOF-TENG). Copper sheets and Kapton films were used as the conductive layer and charge storage layer, respectively. Crystalline powder material (Co-MOF-based triboelectric nanogenerator material) and polyvinylidene fluoride (PVDF) served as the counter electrode friction layer. The PVDF counter electrode was placed in face-to-face contact. Two circular, folded copper wires were connected to the two ends of a Stanford Research Systems SR570 low-noise current amplifier. A SUTP voice coil motor from Wanzhida Motor Manufacturing Co., Ltd. was used to simulate mechanical energy of varying frequencies. The vertical contact-separation triboelectric nanogenerator was constructed through impact. Under continuous, cyclical external force, the distance between the two friction layers varied periodically, resulting in a potential difference. This potential difference then drove the induced electrons to flow periodically, generating a periodic AC pulse output.

[0068] The current, charge density, electric power density and lighting conditions of the Co-MOF-TENG were tested. The results showed that Co-MOF can be used as a triboelectric nanomaterial to effectively utilize mechanical energy.

[0069] 1. Short-circuit current of the Co-MOF triboelectric generator assembled in Example 2

[0070] At room temperature, a SUTP model voice coil motor from Wanzhida Motor Manufacturing Co., Ltd. was used to simulate mechanical energy at different frequencies. Two copper wires were then connected to the two ends of a SR570 model low-noise current amplifier produced by Stanford Research Systems to collect short-circuit current signals such as Figure 12 As shown in the figure, under 5Hz operation, the short-circuit current is 90.59μA. The charge density per unit area σ is integrated from the curve of time and current under 5Hz operation. Calculated, such as Figure 13 As shown, the charge density can reach 134.6 μC·m -2 .

[0071] 2. Open circuit voltage of the Co-MOF triboelectric generator assembled in Example 2

[0072] First, crushed Co-MOF powder was coated on a 5cm×5cm copper sheet. Then, a 5cm×6cm copper sheet was adhered to the counter electrode as a conductive layer. Copper wires were fixed to the copper sheet using conductive silver epoxy. At room temperature, a SUTP model voice coil motor from Wanzhida Motor Manufacturing Co., Ltd. was used to simulate mechanical energy at different frequencies. The two copper wires were then connected to the two ends of a 2657A high-power digital source meter produced by Tektronix to collect open-circuit voltage signals, such as Figure 14 As shown, the open circuit voltage is 469.12V under 5Hz working conditions.

[0073] 3. Power density of the Co-MOF triboelectric generator assembled in Example 2

[0074] At room temperature, a SUTP model voice coil motor from Wanzhida Motor Manufacturing Co., Ltd. was used to simulate mechanical energy at a frequency of 5 Hz. Two copper wires were then connected to a Stanford Research Systems SR570 low-noise current amplifier to collect the short-circuit current signal. The current I was measured with external load resistors of varying resistances from 1 kΩ to 1 GΩ, and the power per unit area (W) was calculated as I. 2 R / S, such as Figure 15 As shown, the power density reaches 3328.49mW / m 2 .

[0075] 4. Stability of the Co-MOF triboelectric generator assembled in Example 2

[0076] The Co-MOF triboelectric generator assembled in Example 2 was operated for a long time to monitor the change of current. The specific method was the same as above. Figure 16 As shown, it shows good output stability.

[0077] 5. The LED light of the Co-MOF triboelectric generator assembled in Example 2 is lit

[0078] At room temperature, a SUTP voice coil motor from Wanzhida Motor Manufacturing Co., Ltd. was used to simulate mechanical energy at a frequency of 5 Hz. Two copper wires were then connected to a rectifier to convert the AC power into DC power. Finally, the wires on the rectifier were connected to the LED light board to test the lighting of the LED light. Figure 17 As shown, it can easily light up 1000 LED lights.

[0079] Example 3

[0080] Example 2 Application of the assembled Co-MOF triboelectric generator for self-powered degradation of organic dyes

[0081] At room temperature, a SUTP voice coil motor from Wanzhida Motor Manufacturing Co., Ltd. was used to simulate mechanical energy at a frequency of 5 Hz. Driven by the Co-MOF-TENG device, a two-electrode system was used to electrochemically degrade organic pollutants. Platinum sheets and straw biochar materials served as cathode and anode, with an electrode spacing of 1.5 cm. A 0.07 M sodium sulfate solution was used as the initial simulated treatment solution. Two copper wires were connected to a rectifier to convert alternating current into direct current, promoting coupling with the electrochemical degradation system. Figure 18As shown,

[0082] The device can complete the degradation of organic dyes. Figure 19 As shown, under 5Hz operation, the characteristic peak of MB (662nm) gradually decreases with time. Within 90 minutes, the Co-MOF-TENG achieves a degradation rate of methylene blue of up to 98.8%, and the solution containing organic pollutants becomes almost clear. In the absence of Co-MOF-TENG, the concentration of methylene blue remains almost unchanged, further demonstrating that Co-MOF can be used as a highly efficient filler to improve the output performance of triboelectric nanogenerators. It also shows that the Co-MOF-TENG has good output stability, laying the foundation for commercial applications.

[0083] The above embodiments describe the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for illustrating the principles of the present invention. Without departing from the scope of the principles of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of protection of the present invention.

Claims

1. A Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid, characterized in that: The chemical formula of the Co-MOF material is {[Co 1.5 (L)(4,4'-azobpy)(H2O)]·6.5H2O} n , n is a non-zero natural number, and L is 1-aminobenzene-3,4,5-tricarboxylic acid.

2. The Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid according to claim 1, characterized in that: The Co-MOF material is a crystalline material, belonging to the monoclinic system, space group C 2 / c， The unit cell parameters are a = 30.345(1)Å, b = 10.008(8)Å, c = 22.750(7)Å, α = 90 o , β = 124.31(3) o , γ = 90 o , whose smallest structural unit consists of 1.5 Co 2+ , 1 L 3- , 1 4,4'-azopyridine, a coordinated water molecule and 7 guest water molecules.

3. The method for preparing the Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid according to claim 1, characterized in that The method comprises the following steps: sealing a mixture of cobalt acetate, 4,4'-azobipyridine, acetonitrile and water in a 10 mL glass vial, fully shaking the mixture in an ultrasonic cleaner until it is completely dissolved, and then placing the mixture in an oven for hydrothermal reaction A. After the reaction is completed, the glass vial is taken out, and a mixture of 1-aminobenzene-3,4,5-tricarboxylic acid and water is added, stirred and adjusted to pH = 9, and the mixture is further sealed in the oven for hydrothermal reaction B. The mixture is then slowly cooled to room temperature to obtain purple block crystals, which are washed with mother liquor and dried to obtain a Co-MOF-based triboelectric material.

4. The method for preparing the Co-MOF material according to claim 1, wherein: The molar ratio of the cobalt acetate, 4,4'-azobipyridine and 1-aminobenzene-3,4,5-tricarboxylic acid is 2:1:

1.

5. The method for preparing the Co-MOF material according to claim 1, wherein: The volume ratio of acetonitrile to water is 1:

2. Based on 0.1 mmol of cobalt acetate, 2 mL of acetonitrile and 4 mL of water are required.

6. The method for preparing the Co-MOF material according to claim 1, wherein: The temperature of the hydrothermal reaction A is 100° C., and the time of the hydrothermal reaction A is 24 hours.

7. The method for preparing the Co-MOF material according to claim 1, wherein: In the mixture of 1-aminobenzene-3,4,5-tricarboxylic acid and water, the concentration of 1-aminobenzene-3,4,5-tricarboxylic acid is 0.05 mol / L, and the pH is adjusted to 9 using 2M sodium hydroxide solution.

8. The method for preparing the Co-MOF material according to claim 1, wherein: The temperature of the hydrothermal reaction B is 100° C., the time of the hydrothermal reaction B is 24 hours, and the cooling rate when cooling to room temperature is 15° C. / h.

9. Use of the Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid according to claim 1 or 2 in constructing a vertical contact-separation triboelectric nanogenerator, characterized in that: Co-MOF material was used as a triboelectric nanogenerator (TENG) to construct a Co-MOF-TENG. Copper sheet and Kapton film were used as the conductive layer and charge storage layer, respectively. Co-MOF and polyvinylidene fluoride were used as the friction layer. After 50,000 cycles, the current could stably reach 90.59 μA, the open circuit voltage reached 469.12 V, and the charge density could reach 134.6 μC·m -2 , the power density reaches 3328.49 mW / m 2 above.

10. Application of the Co-MOF-TENG constructed with the Co-MOF material based on 1-aminobenzene-3,4,5-tricarboxylic acid according to claim 1 or 2 in the degradation of organic pollutants, characterized in that: Driven by the Co-MOF-TENG device, a two-electrode system was used to electrochemically degrade organic pollutants, in which straw biochar material and platinum sheet served as the anode and cathode, with an electrode spacing of 1.5 cm. A 0.07M sodium sulfate solution was used as the initial simulation treatment solution, and two copper wires were connected to a rectifier to integrate AC power into DC power to promote its coupling with the electrochemical degradation system. When the friction nanogenerator Co-MOF-TENG device operated at 5Hz, the device achieved an efficient degradation of methylene blue by 98.8% within 90 minutes.

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