Device and method for self-driven plasma-assisted MOF material detoxification of gastrointestinal toxins

Abstract

This invention discloses a device and method for decontaminating chemical toxins using a self-driven plasma synergistic MOF material. The device comprises a triboelectric nanogenerator power supply system and a chemical toxin decontamination system. The triboelectric nanogenerator power supply system serves as the plasma excitation power source, effectively solving the shortcomings of traditional plasma excitation power sources, such as high energy consumption and lack of portability. The plasma electrode is a plate electrode, and MOF material UiO-66-NH2 is grown on its surface using a hydrothermal method, effectively overcoming the problems of inconvenient collection and environmental pollution after MOF material use. MOFs can efficiently adsorb chemical toxins, but the degradation time is relatively long. Plasma can rapidly degrade chemical toxins that have entered the pores. Simultaneously, the highly porous and ordered crystal structure of the MOF material effectively enhances the plasma discharge electric field. The synergistic effect of these two factors can effectively improve the decontamination efficiency of chemical toxins, playing an important role in rapid on-site disposal and emergency rescue applications.

Description

Technical Field

[0001] This invention belongs to the field of environmental protection, and specifically relates to a device and method for washing away chemical toxins using self-driven plasma and MOFs materials. Background Technology

[0002] Chemical toxins are characterized by their high toxicity, rapid action, long-lasting effects, and wide range of lethality. Nerve agents are a class of highly toxic chemicals, characterized by their extreme toxicity and rapid action. Organophosphorus compounds such as malathion and methylparaoxon (DMNP) are commonly used as mimics for nerve agents; malathion is often used as a mimic for nerve agents like VEX, and DMNP is often used as a mimic for sarin. In addition, malathion and DMNP are also components of organophosphorus pesticides. Due to their outstanding effectiveness in pest control and their cost-effectiveness, organophosphorus pesticides account for more than 50% of most commercially used pesticides, and approximately one-third of the increase in global agricultural output depends on pesticide use. While bringing huge economic benefits, organophosphorus pesticides also bring many risks. Residues of organophosphorus pesticides are extremely toxic to mammals, and their residues in the environment cause serious damage to ecosystems and significant agricultural and environmental pollution. Therefore, there is an urgent need to develop a rapid and effective method to degrade these chemical toxins. Traditional chemical decontamination methods, such as pyrolysis, hydrolysis, oxidation, and physical or chemical adsorption materials, have many shortcomings, including low degradation efficiency, secondary environmental pollution, and cumbersome operation. With societal development, chemical decontamination technologies have demanded high efficiency, convenience, safety, and environmental friendliness. Among numerous decontamination technologies, atmospheric pressure low-temperature plasma and MOF (Metal-Oxide-Factory) material decontamination technologies have received widespread attention.

[0003] Low-temperature plasma, with its broad spectrum, high efficiency, and environmentally friendly nature, has been proven to be an effective method for decontaminating chemical poisons and their mimics, making it a promising chemical decontamination technology. Low-temperature plasma exists in a non-equilibrium state, with its ion temperature much lower than its electron temperature, maintaining strong chemical reactivity while exhibiting a low-temperature state. The high-energy electrons and active free radicals generated by the plasma interact with chemical agent molecules, decomposing or oxidizing the poison molecules into other substances through chemical bond breaking or oxidation. In recent years, plasma has attracted the attention of researchers as an emerging and highly efficient decontamination technology. Yi et al. used an atmospheric pressure plasma jet array to decontaminate malathion and aniline. At an input power of 22.5 W, 20.4 mg of aniline was completely removed after 3 min of He plasma jet treatment; after the introduction of oxygen and water vapor, 1.2 mg of malathion was completely removed within 20 min (Zhihao Yi, Likun Chen, Yashuang Ren, et al. Decontamination of aniline and malathion on material surface by array cold atmospheric pressure plasma jet: Mechanism and decontamination pathways. Journal of Environmental Chemical Engineering, 2022, 10, 107383). Fang et al. used dielectric barrier discharge to remove DMNP. Under the conditions of plasma discharge power of 36.6 W, AC power frequency of 9.27 kHz, and helium gas at 0.5 L / min as the working gas, 3 mL of 200 mg / L DMNP could achieve a degradation rate of about 90% within 2 min. (CaoFang, ShenhaoWang, Changsheng Shao et al. Study of detoxification of methylparathion by dielectric barrier discharge (DBD) non-thermal plasma at gas-liquid interface: mechanism and bio-toxicity evaluation. Journal ofChemosphere, 2022, 11, 135620).Chen et al. used a triboelectric nanogenerator power supply system to deionize the mustard gas mimic 2-chloroethyl ethyl sulfide (2-CEES) using a needle-plate electrode method. They compared the effects of different discharge modes, AC, positive bias, and negative bias, on the degradation efficiency of 2-CEES. Under negative bias, more high-energy electrons and active materials were generated in the plasma, and the energy utilization efficiency was an order of magnitude higher than that of commercial power supplies. (Yuan Bai, Shubin Chen, Huiyan Wang et al. Chemical warfare agents decontamination via air mircoplasma excited by a triboelectric nanogenerator, 2022, 95, 106992) Chen et al. used a triboelectric nanogenerator-powered system to decontaminate 40 μL of 100 mg / L 2-CEES, malathion, and dimethyl methylphosphonate (DMMP) with a negative bias voltage on the needle-plate electrode. Under the condition of an average input power of 0.116 W, the decontamination rate of 2-CEES reached 100% within 3 min. After 7 min of plasma treatment, the decontamination rate of malathion reached 65%, and the decontamination rate of DMMP reached 60%. (Shubin Chen, Shiyu Wang et al. Multiple chemical warfare agents simulants decontamination by self-driven microplasma, 2023, 25(11)) Although the plasma decontamination technology used in the above literature has good effect, it has high energy consumption and the power supply is not portable. Using a triboelectric nanogenerator (TGN) system with a negative bias on needle-plate electrodes for decontamination of chemical toxins presents limitations. These limitations stem from the low power output of the TGN system and the differences in molecular structure and decontamination mechanisms among various chemical toxins. For example, malathion and DMMP are difficult to remove due to the stability of their P=S and P=O bonds, respectively. While the TGN system offers advantages such as portability and high energy efficiency, it has limitations in decontaminating organophosphorus compounds containing highly stable P=S and P=O bonds.

[0004] Metal-organic frameworks (MOFs) exhibit broad activity against a variety of chemical poisons. Katz et al. first used UiO-66 as a solid catalyst to catalyze the hydrolysis of DMNP in 0.45 mol / L N-ethylmorpholine buffer (pH=10) at room temperature, with a degradation half-life (t) 1 / 2The reaction time was 45 min (Katz MJ, Mondloch JE, Totten RK, et al. Simple and compelling biomimetic metal-organic framework catalyst for the degradation of nerve agent simulants. Angewandte Chemie: International Edition, 2014, 53(2): 497-501). Zhao et al. prepared PA-6@TiO2@UiO-66-NH2 nanofiber membranes by electrospinning, atomic layer deposition and solvothermal methods. This material showed extremely strong catalytic hydrolysis ability for the nerve agent soman (O-Pinacolylmethylphosphonofluoridate, GD). 1 / 2 The degradation time is 2.3 min, and the degradation efficiency can reach 100% (15 min) (ZHAO J, Lee DT, Yaga RW, et al. Ultra-fast degradation of chemical warfare agents using MOF-nanofiber kebabs. Angewandte Chemie: International Edition, 2016, 55(42): 13224-13228). However, its microcrystalline powder morphology has problems such as difficult processing and shaping, and difficult transfer in practical applications. It is prone to agglomeration during use and has the disadvantage of being difficult to recycle. It is difficult to directly apply it to the degradation of chemical toxins. Therefore, the combination of metal-organic framework materials with other flexible / rigid materials is a future research hotspot. At present, there are no devices or specific composite materials for the decontamination of chemical toxins using MOFs. Therefore, it is necessary to develop equipment that can be used for surface decontamination, purification of contaminated water, etc., based on the properties of MOFs, and prepare devices that can be applied in practice. Based on the properties of MOFs, uniformly and stably loading them onto metal materials to promote their practical application is of great research significance.

[0005] While atmospheric pressure cryogenic plasma and MOF (Metal-Oxide-Factory) decontamination techniques offer good decontamination effects, the former suffers from high power consumption and the power source is not easily portable due to power supply limitations. Triboelectric nanogenerators (TGNs) power-excited plasma overcome these issues, but their structural limitations result in lower output current and lower plasma energy. Therefore, their decontamination efficiency is limited for certain chemical toxins, such as organophosphorus compounds containing relatively stable P=S and P=O bonds, like malathion and DMMP. MOF materials are often used directly in microcrystalline powder form mixed with toxic compounds, exhibiting significant adsorption effects, but their degradation time is long, and they are difficult to recycle after use, leading to secondary pollution. Summary of the Invention

[0006] To address the above problems, this invention proposes growing MOFs (Metal-O-Film) materials on the surface of a plasma discharge electrode. Through the synergistic catalysis of plasma discharge and MOFs, efficient degradation of chemical toxins can be achieved. MOFs are highly porous and ordered crystal structures capable of efficiently adsorbing chemical toxins, but they suffer from long degradation times and difficulty in recycling. By growing the MOF material UiO-66-NH2 on the surface of the plasma electrode, the problems of inconvenient collection and environmental pollution after use of MOF materials are effectively overcome. Plasma can rapidly degrade chemical toxins that have entered the pores. Simultaneously, the highly porous and ordered crystal structure of the MOF material effectively enhances the plasma discharge electric field. The synergistic effect of these two factors can effectively improve the decontamination efficiency of chemical toxins, playing a crucial role in rapid on-site disposal and emergency rescue applications.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A self-driven plasma-assisted MOF material detoxification device for gastrointestinal poisons includes:

[0009] The triboelectric nanogenerator power supply system consists of a stator, an intermediate isolation layer, a rotor, and a drive unit. The stator uses a first acrylic plate as a substrate, on which twelve 1 / 12th-sized sector-shaped aluminum films are uniformly bonded. The metal sector areas at opposite central angles of the sector-shaped aluminum films are interconnected, forming alternating metal electrodes. The rotor uses a second acrylic plate as a substrate, on which six sector-shaped polytetrafluoroethylene (PTFE) films are uniformly bonded. The intermediate isolation layer consists of four long paper strips, each a three-folded tissue paper, which replenishes triboelectric charge while preventing direct hard contact between the stator and rotor, thus allowing the device to maintain high performance over a long period.

[0010] Chemical decontamination system: Composed of a bridge rectifier, needle plate electrodes, and a decontamination chamber. The bridge rectifier consists of four voltage-resistant diodes. The needle plate electrodes consist of tungsten needles and an aluminum flat-bottomed container. MOF material UiO-66-NH2 is grown hydrothermally at the bottom of the aluminum flat-bottomed container, the steps of which are as follows:

[0011] Step 1: Remove surface impurities from the aluminum flat-bottomed container and etch the bottom of the aluminum flat-bottomed container using plasma jet etching;

[0012] Step 2: Add deionized water and ethanol to the blue-capped bottle, then add zirconium chloride and sonicate until homogeneous. Continue by adding 2-aminoterephthalic acid and sonicating until completely dissolved. Finally, add acetic acid and hydrochloric acid and sonicate until homogeneous.

[0013] Step 3: Place the aluminum flat-bottomed container etched in Step 1 into the mixed solution obtained in Step 2, seal it completely, and then heat it to react;

[0014] Step 4: After the reaction is complete, cool to room temperature, take out the aluminum flat-bottomed container from Step 3, rinse with deionized water, soak in ethanol several times, and then vacuum dry to obtain an aluminum flat-bottomed container with UiO-66-NH2 loaded at the bottom.

[0015] The chemical poison is placed in an aluminum flat-bottomed container loaded with UiO-66-NH2 at the bottom. Tungsten needles are placed vertically at a certain distance from the aluminum flat-bottomed container to form a needle plate electrode, which is then placed in the decontamination chamber to form a chemical poison decontamination system.

[0016] The triboelectric nanogenerator power supply system connects the bridge rectifier and the needle plate electrode, including but not limited to using an electric motor as the driving force to achieve relative rotation between the rotor and stator to generate electrical energy. Starting the triboelectric nanogenerator power supply system initiates the degradation of chemical toxins.

[0017] This invention employs a high-output-voltage self-driven triboelectric nanogenerator power supply system to replace the traditional high-voltage power supply. Its output voltage can reach 3000-4000 V, exciting the needle-plate electrodes to generate plasma, which can produce high concentrations of O3, OH, and other compounds. 1 Active substances such as O2 have good decontamination performance against chemical toxins; MOF material UiO-66-NH2 is grown on the surface of plate electrodes using a hydrothermal method, which works in conjunction with plasma to decontaminate chemical toxins.

[0018] The grown MOFs materials not only have good decontamination performance, but their micro-nano structures can effectively enhance the electric field and improve the discharge performance of plasma. At the same time, the porous structure can greatly increase the contact area between active substances and chemical agents, further improving the decontamination performance. The triboelectric nanogenerator power supply system, as a power source, gives the decontamination device advantages such as self-driving, portability, greenness, and high efficiency, greatly expanding its application scenarios.

[0019] As a preferred technical solution, the stator substrate material of the triboelectric nanogenerator power supply system is an acrylic sheet.

[0020] Preferably, the base dimensions of the stator are an outer diameter of 400mm, an inner diameter of 25mm, and a thickness of 8mm.

[0021] As a preferred technical solution, the manufacturing of the triboelectric nanogenerator power supply system involves bonding metal electrodes onto the stator of the triboelectric nanogenerator power supply system.

[0022] Preferably, the metal electrode is made of aluminum foil with a thickness of 0.05 mm. The aluminum foil is cut into twelve 1 / 12 fan-shaped sections. Opposite metal fan-shaped sections are connected to each other to form alternating metal electrodes, and the aluminum foil is bonded to the stator.

[0023] As a preferred technical solution, the rotor substrate material of the triboelectric nanogenerator power supply system is an acrylic sheet.

[0024] Preferably, the rotor has an outer diameter of 400mm, an inner diameter of 15mm, and a thickness of 3mm.

[0025] As a preferred technical solution, the manufacturing of the triboelectric nanogenerator power supply system involves bonding a friction layer onto the rotor of the triboelectric nanogenerator power supply system.

[0026] Preferably, the friction layer is made of polytetrafluoroethylene film with a thickness of 0.2 mm. The polytetrafluoroethylene film is cut into six fan shapes and evenly bonded to the rotor surface.

[0027] As a preferred technical solution, the manufacturing of the triboelectric nanogenerator power supply system involves designing an intermediate spacer layer between the stator and rotor.

[0028] Preferably, the intermediate spacer layer is a paper towel folded three times, in total, four strips, each 180mm long and 15mm wide, and evenly adhered to the stator surface.

[0029] As a preferred technical solution, the bridge rectifier in the manufacturing of the chemical decontamination system consists of four voltage-resistant diodes.

[0030] Preferably, the withstand voltage diode is model R5000, DO-1.

[0031] As a preferred technical solution, in the manufacture of the chemical decontamination system, the plasma discharge electrode is a needle plate electrode, which consists of a tungsten needle and an aluminum flat-bottomed container.

[0032] Preferably, the tip curvature radius of the tungsten needle is 0.15-0.25 mm.

[0033] Preferably, the aluminum flat-bottomed container has a diameter of 6.7 mm, a height of 6 mm, and a thickness of 0.2 mm.

[0034] Preferably, in step one, the method for removing surface impurities from the aluminum flat-bottomed container involves ultrasonically cleaning the container with acetone and ethanol 3-5 times, preferably 5 times. The etching method involves using a commercial AC power supply to excite an argon plasma jet to etch the bottom of the aluminum flat-bottomed container. The power is 20-30 W, for example, 20 W, 23 W, 27 W, 30 W, etc., with a gas flow rate of 2-5 L / min, for example, 2 L / min, 3 L / min, 5 L / min, and a distance from the substrate of 4-10 mm, for example, 4 mm, 6 mm, 8 mm, 10 mm. A preferred etching method is: power 27 W, gas flow rate 3 L / min, and a distance from the substrate of 5 mm.

[0035] Preferably, the solution preparation method in step two is as follows: Add 15-25 mL of deionized water, preferably 20 mL, and 15-25 mL of ethanol, preferably 20 mL, to a blue-capped bottle. Add 0.5-0.7 g of zirconium chloride, preferably 0.64 g. After addition, sonicate for 10-20 min until homogeneous, preferably 15 min. After sonication, add 0.4-0.6 g of 2-aminoterephthalic acid, preferably 0.464 g. Continue sonicating for 10-20 min until completely dissolved, preferably 15 min. After complete dissolution, add 10-40 mL of acetic acid, for example, 10 mL, 20 mL, 30 mL, 40 mL, etc., preferably 20 mL; add 0-200 μL of hydrochloric acid, for example, 0 μL, 100 μL, 200 μL, etc., preferably 100 μL. Sonicate for 10-20 min until homogeneous, preferably 15 min.

[0036] Preferably, the heating reaction in step three is carried out in a forced-air drying oven at a heating temperature of 80-100 ℃, preferably 90 ℃; and the reaction time is 8-24 h, preferably 24 h.

[0037] Preferably, in step four, the rinsing is performed 2-3 times with deionized water, preferably 3 times. The ethanol soaking process lasts 16-32 hours, for example, 16 hours, 24 hours, or 32 hours, preferably 24 hours, with fresh ethanol replaced every 8 hours. Drying is carried out in a vacuum drying oven for 16-32 hours, preferably 24 hours; the drying temperature is 70-90 °C, preferably 85 °C.

[0038] Preferably, the needle electrode and the bottom of the aluminum flat-bottomed container are placed vertically with a gap of 0.5-1.5 mm, such as 0.5 mm, 1 mm, 1.5 mm, etc., preferably 1 mm.

[0039] Preferably, the volume of the decontamination chamber is 250 mL.

[0040] Preferably, the two output terminals of the triboelectric nanogenerator power supply system are connected to a bridge rectifier via wires and then connected to the needle electrode and the plate electrode in the form of negative bias.

[0041] As a preferred technical solution, the chemical toxins used in the device manufacturing and decontamination method of the present invention are nerve agent mimics and organophosphorus pesticide components, with DMNP and malathion being preferred as the subjects of investigation.

[0042] Preferably, the volume of the chemical poison is 20-60 μL, such as 20 μL, 40 μL, 60 μL, etc., preferably 40 μL; the concentration is 50-150 mg / L, such as 50 mg / L, 100 mg / L, 150 mg / L, preferably 100 mg / L.

[0043] Preferably, the degradation time is 0-10 min, for example 0 min, 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, and preferably 7 min. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the self-driven plasma-assisted MOFs material decontamination device in the embodiment;

[0045] 1. First acrylic sheet; 2. Fan-shaped aluminum film; 3. Intermediate insulating layer; 4. Second acrylic sheet; 5. Fan-shaped polytetrafluoroethylene film; 6. Bridge rectifier; 7. Tungsten needle; 8. Decontamination chamber; 9. Aluminum flat-bottomed container;

[0046] Figure 2 A process flow diagram for MOF growth;

[0047] Figure 3 This is a scanning electron microscope image of the bottom of an etched aluminum flat-bottomed container.

[0048] Figure 4 Scanning electron microscope image of the bottom of the flat-bottomed aluminum container used for growing MOF material UiO-66-NH2;

[0049] Figure 5 Voltage and current diagrams of plasma discharge under different needle-plate spacings;

[0050] Figure 6 The decontamination rate curve of DMNP for a self-driven plasma-assisted MOF material decontamination device;

[0051] Figure 7 The decontamination rate curve of malathion by a self-driven plasma-assisted MOF material decontamination device. Detailed Implementation

[0052] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely for aiding understanding and should not be considered as specific limitations of the invention.

[0053] The embodiments of the present invention are as follows:

[0054] A self-driven plasma-assisted MOFs material device and method for detoxifying chemical poisons, the preparation and detoxification process of which includes the following steps:

[0055] like Figure 1 As shown, the triboelectric nanogenerator power supply system is fabricated as follows: The triboelectric nanogenerator power supply system consists of a stator, an intermediate isolation layer 3, a rotor, and a drive device. The stator is based on a first acrylic plate 1, on which twelve 1 / 12th-sized sector-shaped aluminum films 2 are uniformly bonded. Opposite metal sector areas of the sector-shaped aluminum films 2 are interconnected, forming alternating metal electrodes. The rotor is based on a second acrylic plate 4, on which six sector-shaped polytetrafluoroethylene films 5 are uniformly bonded. The intermediate isolation layer 3 consists of four long paper strips, which are paper towels folded three times to their thickness. These strips supplement triboelectric charge while preventing direct hard contact between the stator and rotor, thus allowing the device to maintain high performance over a long period.

[0056] Preparation of the chemical decontamination system: The chemical decontamination system consists of a bridge rectifier 6, a needle plate electrode, and a decontamination chamber 8. The bridge rectifier 6 consists of four voltage-resistant diodes. The needle plate electrode consists of tungsten needles 7 and an aluminum flat-bottomed container 9. MOF material UiO-66-NH2 is grown at the bottom of the aluminum flat-bottomed container 9, and the steps are as follows:

[0057] Step 1: Remove surface impurities from the aluminum flat-bottomed container 9, such as... Figure 2 As shown, the bottom of the aluminum flat-bottomed container 9 is etched using plasma jet etching; as... Figure 3 As shown;

[0058] Step 2: Add deionized water and ethanol to the blue-capped bottle, then add zirconium chloride and sonicate until homogeneous. Continue by adding 2-aminoterephthalic acid and sonicating until completely dissolved. Finally, add acetic acid and hydrochloric acid and sonicate until homogeneous.

[0059] Step 3: Place the aluminum flat-bottomed container 9 (etched in Step 1) into the mixed solution obtained in Step 2, seal it completely, and then heat it to react;

[0060] Step 4: After the reaction is complete, cool to room temperature, remove the aluminum flat-bottomed container 9 from Step 3, rinse with deionized water, soak repeatedly in ethanol, and then vacuum dry to obtain the following... Figure 4 The aluminum flat-bottomed container 9 shown is loaded with UiO-66-NH2 at the bottom;

[0061] The chemical poison is placed in an aluminum flat-bottomed container 9 with a bottom load of UiO-66-NH2. Tungsten needles 7 are placed vertically at a certain distance from the aluminum flat-bottomed container 9 to form a needle plate electrode, which is placed in the decontamination chamber 8 to form a chemical poison decontamination system.

[0062] The triboelectric nanogenerator power supply system connects the bridge rectifier 6 and the needle plate electrode, using an electric motor as the driving force to achieve relative rotation between the rotor and stator. Starting the triboelectric nanogenerator power supply system initiates the degradation of chemical toxins.

[0063] The chemical toxins included nerve agent mimics and organophosphorus pesticide components, with DMNP and malathion being the preferred targets.

[0064] Example 1:

[0065] On the stator substrate of the first acrylic plate 1 with an outer diameter of 400mm, an inner diameter of 25mm, and a thickness of 8mm, an aluminum foil with a thickness of 0.05mm is bonded as a metal electrode. The aluminum foil is cut into twelve 1 / 12 fan-shaped aluminum films 2. The metal fan-shaped areas in opposite positions are connected to each other to form alternating metal electrodes.

[0066] On the rotor base of the second acrylic plate 4 with an outer diameter of 400mm, an inner diameter of 15mm, and a thickness of 3mm, a 0.2mm thick polytetrafluoroethylene (PTFE) film is bonded as a friction layer. The PTFE film is cut into six fan-shaped PTFE films 5 and uniformly bonded to the rotor surface. The driving device includes, but is not limited to, using an electric motor (180 W, 240 VDC, 600 rpm) to provide power to the triboelectric nanogenerator system.

[0067] Four 180mm long and 15mm wide paper towels, folded three times, are used as the middle isolation layer 3 and are evenly adhered to the surface of the stator.

[0068] Four voltage-resistant diodes R5000 and DO-1 are connected to form a bridge rectifier 6. The two poles of the metal electrodes of the triboelectric nanogenerator power supply system are connected to the bridge rectifier 6 through wires. The bridge rectifier 6 is connected to a tungsten needle 7 with a tip curvature radius of 0.15-0.25 mm and an aluminum flat-bottomed container 9 with a diameter of 6.7 mm, a height of 6 mm, and a thickness of 0.2 mm, on which MOFs material UiO-66-NH2 is grown at the bottom.

[0069] The method for growing MOFs material on the bottom surface of aluminum flat-bottomed container 9 is as follows:

[0070] An aluminum flat-bottomed container 9 with a diameter of 6.7 mm, a height of 6 mm, and a thickness of 0.2 mm was ultrasonically cleaned 5 times with acetone and ethanol, respectively.

[0071] A commercial AC power supply was used to excite an argon plasma jet to etch the bottom of an aluminum flat-bottomed container 9. The power was 27 W, the gas flow rate was 3 L / min, and the distance from the substrate was 5 mm.

[0072] Add 20 mL of deionized water and 20 mL of ethanol to the blue-capped bottle;

[0073] Add 0.64 g of zirconium chloride to a mixed solution of deionized water and ethanol, and sonicate for 15 min until homogeneous;

[0074] Add 0.464 g of 2-aminoterephthalic acid to a mixed solution containing zirconium chloride and sonicate for 15 min until completely dissolved;

[0075] Add 20 mL of acetic acid and 100 μL of hydrochloric acid to the mixed solution and sonicate for 15 min until homogeneous;

[0076] The etched aluminum flat-bottomed container 9 was placed in the mixed solution, sealed completely, and heated in a forced-air drying oven for 24 h at a temperature of 90 °C.

[0077] After the reaction was completed, the container was cooled to room temperature, and the aluminum flat-bottomed container 9 was removed. It was rinsed three times with deionized water, soaked in ethanol for 24 h, and fresh ethanol was replaced every 8 h. Then it was vacuum dried in a vacuum drying oven for 24 h at a temperature of 85 ℃ to obtain the aluminum flat-bottomed container 9 with UiO-66-NH2 loaded at the bottom.

[0078] The needle electrode and the aluminum flat-bottomed container 9 loaded with MOFs are placed vertically at a distance of 1 mm to form a needle plate electrode, which is placed in the decontamination chamber 8.

[0079] A 40 μL volume of DMNP at a concentration of 100 mg / L was placed in an aluminum flat-bottomed container 9, and a triboelectric nanogenerator power supply system was activated for degradation treatment for 7 min. The aluminum flat-bottomed container 9, with MOF material UiO-66-NH2 grown on it, was used as a plate electrode, forming a plasma discharge electrode with a 7-pin tungsten needle electrode, and powered by a triboelectric nanogenerator power supply system. Figure 5 As shown. Its rinsing efficiency against 40 μL of 100 mg / L DMNP is as follows. Figure 6 As shown, the DMNP was 100% cleaned up after 7 min, and the energy utilization efficiency was 0.042 μg / J, indicating that the cleaned up method has excellent cleaned up performance for DMNP.

[0080] Example 2:

[0081] On the stator substrate of the first acrylic plate 1 with an outer diameter of 400mm, an inner diameter of 25mm, and a thickness of 8mm, an aluminum foil with a thickness of 0.05mm is bonded as a metal electrode. The aluminum foil is cut into twelve 1 / 12 fan-shaped aluminum films 2. The metal fan-shaped areas in opposite positions are connected to each other to form alternating metal electrodes.

[0082] On the rotor base of the second acrylic plate 4 with an outer diameter of 400mm, an inner diameter of 15mm, and a thickness of 3mm, a 0.2mm thick polytetrafluoroethylene (PTFE) film is bonded as a friction layer. The PTFE film is cut into six fan-shaped PTFE films 5 and uniformly bonded to the rotor surface. The driving device includes, but is not limited to, using an electric motor (180W, 240VDC, 600rpm) to provide power to the triboelectric nanogenerator system.

[0083] Four 180mm long and 15mm wide paper towels, folded three times, are used as the middle isolation layer 3 and are evenly adhered to the surface of the stator.

[0084] Four voltage-resistant diodes are connected to form a bridge rectifier 6. The two poles of the metal electrodes of the triboelectric nanogenerator power supply system are connected to the bridge rectifier 6 via wires. The bridge rectifier 6 is connected via wires to a tungsten needle 7 with a tip curvature radius of 0.15-0.25 mm, and an aluminum flat-bottomed container 9 with a diameter of 6.7 mm, a height of 6 mm, and a thickness of 0.2 mm, on which MOFs material UiO-66-NH2 is grown at the bottom.

[0085] The method for growing MOFs material on the bottom surface of aluminum flat-bottomed container 9 is as follows:

[0086] An aluminum flat-bottomed container 9 with a diameter of 6.7 mm, a height of 6 mm, and a thickness of 0.2 mm was ultrasonically cleaned 5 times with acetone and ethanol, respectively.

[0087] A commercial AC power supply was used to excite an argon plasma jet to etch the bottom of an aluminum flat-bottomed container 9. The power was 27 W, the gas flow rate was 3 L / min, and the distance from the substrate was 5 mm.

[0088] Add 20 mL of deionized water and 20 mL of ethanol to the blue-capped bottle;

[0089] Add 0.64 g of zirconium chloride to a mixed solution of deionized water and ethanol, and sonicate for 15 min until homogeneous;

[0090] Add 0.464 g of 2-aminoterephthalic acid to a mixed solution containing zirconium chloride and sonicate for 15 min until completely dissolved;

[0091] Add 20 mL of acetic acid and 100 μL of hydrochloric acid to the mixed solution and sonicate for 15 min until homogeneous;

[0092] The etched aluminum flat-bottomed container 9 was placed in the mixed solution, sealed completely, and heated in a forced-air drying oven for 24 h at a temperature of 90 °C.

[0093] After the reaction was completed, the container was cooled to room temperature, and the aluminum flat-bottomed container 9 was removed. It was rinsed three times with deionized water, soaked in ethanol for 24 h, and fresh ethanol was replaced every 8 h. Then it was vacuum dried in a vacuum drying oven for 24 h at a temperature of 85 ℃ to obtain the aluminum flat-bottomed container 9 with UiO-66-NH2 loaded at the bottom.

[0094] The needle electrode and the aluminum flat-bottomed container 9 loaded with MOFs are placed vertically at a distance of 1 mm to form a needle plate electrode, which is placed in the decontamination chamber 8.

[0095] A 40 μL solution of malathion at a concentration of 100 mg / L was placed in an aluminum flat-bottomed container 9, and a triboelectric nanogenerator power supply system was activated for degradation treatment for 7 minutes. The aluminum flat-bottomed container 9, with MOF material UiO-66-NH2 grown on it, was used as a plate electrode, forming a plasma discharge electrode with a tungsten needle electrode 7, and powered by a triboelectric nanogenerator system. Figure 5 As shown. Its scavenging efficiency against 40 μL of 100 mg / L malathion is as follows. Figure 7 As shown, the decontamination rate of malathion reached 94% after 7 min of decontamination, and the energy utilization efficiency reached 0.037 μg / J, indicating that the decontamination method has excellent decontamination performance for malathion.

Claims

1. A device for detoxifying chemical toxins using self-driven plasma-assisted MOF materials, characterized in that: This includes a triboelectric nanogenerator power supply system and a chemical decontamination system; The triboelectric nanogenerator power supply system comprises, from top to bottom, a first acrylic plate (1), a fan-shaped aluminum film (2), an intermediate isolation layer (3), a second acrylic plate (4), and a polytetrafluoroethylene film (5); wherein the first acrylic plate (1) is the base of the stator, and twelve fan-shaped aluminum films (2) are uniformly bonded in a ring on the acrylic plate (1), and the metal fan-shaped areas at opposite central angles of the fan-shaped aluminum films (2) are connected to each other to form alternating metal electrodes; the second acrylic plate (4) is the base of the rotor, and six fan-shaped polytetrafluoroethylene films (5) are uniformly bonded on the second acrylic plate (4); the intermediate isolation layer (3) is composed of four long paper strips forming a cross structure; The chemical decontamination system includes a bridge rectifier (6), a tungsten needle (7), a decontamination chamber (8), and an aluminum flat-bottom container (9). The bridge rectifier (6) is an electronic circuit composed of four voltage-resistant diodes that converts alternating current into direct current. A triboelectric nanogenerator power supply system is connected to the bridge rectifier (6). The electrical energy output by the triboelectric nanogenerator power supply system is output in the form of a negative bias through the bridge rectifier (6). The bridge rectifier (6) is connected to the tungsten needle (7) and the aluminum flat-bottom container (9). The tungsten needle (7) and the aluminum flat-bottom container (9) are placed vertically at a certain distance to form a needle-plate electrode, which is placed inside the decontamination chamber (8). The bottom of the aluminum flat-bottom container (9) is grown with MOF material UiO-66-NH2 by hydrothermal method.

2. The device for detoxifying chemical poisons using self-driven plasma-assisted MOF materials according to claim 1, characterized in that, The outer diameter of the first acrylic sheet (1) is 400mm, the inner diameter is 25mm, and the thickness is 8mm; the outer diameter of the second acrylic sheet (4) is 400mm, the inner diameter is 15mm, and the thickness is 3mm.

3. The device for washing away gastrointestinal toxins using self-driven plasma-assisted MOF materials according to claim 1, characterized in that, The fan-shaped aluminum film (2) has a thickness of 0.05 mm, and the fan-shaped polytetrafluoroethylene film (5) has a thickness of 0.2 mm.

4. The device for washing away gastrointestinal toxins using self-driven plasma-assisted MOF materials according to claim 1, characterized in that, The tungsten needle (7) has a tip curvature radius of 0.15-0.25 mm. The aluminum flat-bottomed container (9) has a diameter of 6.7 mm, a height of 6 mm, and a thickness of 0.2 mm. The tungsten needle (7) is placed vertically with a 1 mm gap between the bottom of the aluminum flat-bottomed container (9) and placed inside the decontamination chamber (8).

5. A method for preparing the device for washing away gastrointestinal toxins using self-driven plasma-assisted MOF materials as described in any one of claims 1 to 4, characterized in that, Includes the following steps: Step 1: Remove surface impurities from the aluminum flat-bottom container (9). The bottom surface of the aluminum flat-bottom container (9) is smooth. The bottom of the aluminum flat-bottom container (9) is etched by plasma jet. The bottom of the aluminum flat-bottom container (9) after plasma etching helps the MOF material grow at the bottom. Step 2: Add deionized water and ethanol to the blue-capped bottle, then add zirconium chloride and sonicate until homogeneous; continue to add 2-aminoterephthalic acid and sonicate until completely dissolved; finally add acetic acid and hydrochloric acid and sonicate until homogeneous. Step 3: Place the aluminum flat-bottomed container (9) etched in Step 1 into the mixed solution obtained in Step 2, seal it completely, and then heat it to react; Step 4: After the reaction is complete, cool to room temperature, take out the aluminum flat-bottom container (9) from step 3, rinse with deionized water, soak in ethanol several times, and then vacuum dry to obtain the aluminum flat-bottom container (9) with UiO-66-NH2 loaded at the bottom. Tungsten needles (7) and aluminum flat-bottomed containers (9) are placed vertically at a certain distance to form needle plate electrodes, and are placed in the decontamination chamber (8) to form a chemical poison decontamination system. The triboelectric nanogenerator power supply system is connected to the bridge rectifier (6) and the needle plate electrode respectively; the motor is used as the driving device, and a keyway is designed on the rotor for the motor to drive the rotor to rotate.

6. The method for preparing the device for washing away gastrointestinal toxins using self-driven plasma-assisted MOF materials according to claim 5, characterized in that, The method for removing surface impurities from the aluminum flat-bottomed container (9) in step one is as follows: the aluminum flat-bottomed container (9) is ultrasonically cleaned 3-5 times with acetone and ethanol respectively. The etching method is as follows: argon plasma jet is used to etch the bottom of the aluminum flat-bottom container (9), with a power of 20-30 W, a gas flow rate of 2-5 L / min, and a distance of 4-10 mm from the substrate.

7. The method for preparing the device for washing away chemical toxins using self-driven plasma-assisted MOF materials according to claim 5, characterized in that, In step two, the amounts of each substance are prepared according to the following proportions: add 15-25 mL of deionized water, 15-25 mL of ethanol, and 0.5-0.7 g of zirconium chloride, and sonicate for 10-20 min until homogeneous; then add 0.4-0.6 g of 2-aminoterephthalic acid, and sonicate for 10-20 min until completely dissolved; finally, add 10-40 mL of acetic acid and 0-200 μL of hydrochloric acid, and sonicate for 10-20 min until homogeneous.

8. The method for preparing the device for washing away gastrointestinal toxins using self-driven plasma-assisted MOF materials according to claim 5, characterized in that, The heating reaction in step three is carried out in a forced-air drying oven at a temperature of 80-100 ℃ for a reaction time of 8-24 h.

9. The method for preparing the device for washing away gastrointestinal toxins using self-driven plasma-assisted MOF materials according to claim 5, characterized in that, In step four, the container is rinsed 2-3 times with deionized water, soaked in ethanol for 16-32 hours, with fresh ethanol replaced every 8 hours, and dried in a vacuum drying oven at a temperature of 70-90 ℃ for 16-32 hours to obtain an aluminum flat-bottomed container (9) with UiO-66-NH2 loaded at the bottom.

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