Micro-nano robot for removing heavy metals and antibiotics in livestock and poultry manure

Abstract

The invention discloses a micro-nano robot for removing heavy metals and antibiotics in livestock and poultry manure. A preparation method comprises the following steps: S1, carrying out ultrasonic cleaning treatment on halloysite nanotubes (HNTs) with water and ethanol; s2, FeCl3. 6H2O, C6H5Na3O7 and NaAc. 3H2O are sequentially added into ethylene glycol, and mixing is carried out under violent stirring; s3, adding the halloysite nanotubes into the mixed solution under continuous stirring, and continuously stirring for 1 hour; the device has autonomous mobility and magnetic response capability, has the advantages of high efficiency, durability and environmental protection, and solves the problems of low removal rate of heavy metals in livestock and poultry manure and incomplete degradation of antibiotics in the traditional pollutant treatment technology.

Description

Technical Field

[0001] The invention relates to the technical field of livestock and poultry waste treatment, and in particular to a micro-nano robot used for removing heavy metals and antibiotics from livestock and poultry excrement. Background Art

[0002] Heavy metals and antibiotics in livestock and poultry manure are difficult to remove, but persist and bioaccumulate. Traditional pollutant treatment technologies control the spread of pollutants to a certain extent, mainly by reducing their bioavailability; however, they have limitations in practical application. The limitations of physical adsorption include adsorbent saturation, limited lifespan and difficulty in recovery, which restrict its application in large-scale pollutant treatment. Chemical precipitation requires a large amount of chemical reagents and poses a risk of secondary pollution. Biodegradation is limited by environmental conditions and has a low pollutant removal rate. Therefore, sustainable, environmentally friendly and efficient pollutant removal methods are needed.

[0003] The emergence of micro-nano robots has provided innovative solutions to environmental pollution problems. The basic research and conceptualization of micro-robots, initiated and classified in the early 1970s, paved the way for the interdisciplinary integration of environmental science and micro / nanotechnology. Micro-nano robots are capable of converting energy into mechanical motion and are micro-devices integrated with nanocomposites with autonomous mobility and intelligent response capabilities. The advantage of micro-nano robots is that they can reduce the dependence on harmful chemicals commonly used in traditional cleaning operations. By applying micro-nano robots, ecological disturbances can be significantly reduced and the negative effects associated with traditional treatment strategies can be effectively mitigated. Most micro-nano robots are recyclable and have high efficiency, environmental friendliness, and durability in the removal of environmental pollutants. Micro-nano robots are able to overcome the limitations of macro robots in specific scenarios (e.g., complex or confined spaces). Their structure, performance, and autonomous mobility overcome the limitations of passive diffusion, facilitate interaction with target pollutants, and perform a range of predetermined tasks, including sensing and removing pollutants from environmental media.

[0004] However, current research on micro-nano robots for pollutant removal mainly focuses on homogeneous wastewater environments. The complexity of livestock and poultry manure, including its heterogeneity and high density, hinders the movement of micro-nano robots. The application of micro-nano robots in such heterogeneous environments is still in the initial exploratory stage. In solid waste treatment, micro-nano robots can quickly recover precious metals from electronic waste, and actively navigate and attach to fibrous waste to accelerate its removal. In soil treatment, micro-nano robots effectively capture and fix heavy metals and promote the removal of organic pollutants through Fenton-like reactions. These studies provide a theoretical basis and technical support for micro-nano robots to remove pollutants in heterogeneous environments. However, a new technical solution is still needed for the treatment of heavy metals and antibiotics in livestock and poultry manure. Summary of the invention

[0005] The purpose of the present invention is to provide a micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure. The present invention has autonomous mobility and magnetic response capabilities, and exhibits the advantages of high efficiency, durability and environmental protection, solving the problems of low heavy metal removal rate and incomplete degradation of antibiotics in livestock and poultry manure caused by traditional pollutant treatment technologies.

[0006] To achieve the above object, the present invention provides the following technical solution: a micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure, the preparation method of which comprises the following steps:

[0007] S1, subjecting the halloysite nanotubes (HNTs) to ultrasonic cleaning with water and ethanol;

[0008] S2, add FeCl3·6H2O, C6H5Na3O7 and NaAc·3H2O to ethylene glycol in sequence and mix under vigorous stirring;

[0009] S3, adding HNTs to the mixed solution under continuous stirring, and continuing stirring for 1 hour;

[0010] S4, transferring the viscous mixed solution to a stainless steel autoclave lined with polytetrafluoroethylene and reacting at high temperature for 12 hours;

[0011] S5, using a permanent magnet to collect the black precipitate in the suspension, and washing it with deionized water and ethanol for multiple times, and drying the washed product in a vacuum to obtain Fe3O4-HNTs;

[0012] S6, disperse the dried Fe3O4-HNTs and KMnO4 in deionized water, stir vigorously at room temperature for 20.0 minutes, add HCl, and continue stirring for 30.0 minutes;

[0013] S7, transferring the mixture into a stainless steel autoclave lined with polytetrafluoroethylene and subjecting it to high temperature treatment for 6 hours, collecting the product by centrifugation after the treatment, washing it with deionized water and ethanol for multiple times and drying it under vacuum to obtain a MnO2-Fe3O4-HNTs micro-nano robot;

[0014] S8, disperse the MnO2-Fe3O4-HNTs micro-nano robots and g-C3N4 nanosheets in distilled water and shake for 12 hours;

[0015] S9, collecting the CN-MnO2-Fe3O4-HNTs micro-nano robots by centrifugation, washing them with deionized water for several times, and drying them under vacuum;

[0016] S10. Use scanning electron microscopy, energy dispersive X-ray spectroscopy, UV-visible absorption spectroscopy, photoluminescence emission spectroscopy, fluorescence microscopy images, X-ray diffraction and Fourier transform infrared spectroscopy to detect the characterization of the micro-nano robot, and adjust and optimize the composition structure, surface morphology and interface morphology of the micro-nano robot to ensure the efficient removal of heavy metals and antibiotics in livestock and poultry manure.

[0017] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, the HNTs in S1 have a length of 3-8 μm and a diameter of 50-200 nm.

[0018] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, the mass ratio of FeCl3·6H2O, C6H5Na3O7 and NaAc·3H2O in S2 is 11:4:33.

[0019] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, the mass ratio of the HNTs in S3 to the FeCl3·6H2O, sodium citrate and NaAc·3H2O in S2 is 1:11:4:33, and the stirring time is 1 hour.

[0020] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, the volume of the polytetrafluoroethylene-lined stainless steel high-pressure reactor in S4 is 100 mL; when performing high-temperature treatment, the reaction temperature is 200° C. and the reaction time is 12 h.

[0021] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, the drying temperature in S5 is -60°C and the drying time is 12 hours.

[0022] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, the mass ratio of Fe3O4-HNTs and KMnO4 in the S6 is 3:7.

[0023] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, the volume of the polytetrafluoroethylene-lined stainless steel high-pressure reactor in S7 is 50 mL; when performing high-temperature treatment, the reaction temperature is 100° C. and the reaction time is 6 hours.

[0024] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, the mass ratio of the MnO2-Fe3O4-HNTs micro-nano robot and the g-C3N4 nanosheets in S8 is 4:1.

[0025] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, when the micro-nano robot in S9 performs vacuum drying, the drying temperature is -60°C and the drying time is 12 hours.

[0026] As a preferred micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure of the present invention, when detecting the micro-nano robot in S10, the component structure, surface morphology and interface morphology of the micro-nano robot are detected respectively.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] 1. The present invention is highly efficient. By precisely controlling the material ratio and using deionized water to form a uniform suspension, uniform deposition on HNTs is ensured, thereby improving the uniformity and consistency of the micro-nano robot. This uniformity enables the micro-nano robot to more effectively adsorb and degrade target pollutants. The MnO2 layer not only helps to adsorb heavy metal ions, but also enhances the catalytic activity of the micro-nano robot, enabling them to produce reactive oxygen species in the presence of hydrogen peroxide, effectively degrading antibiotics in livestock and poultry manure.

[0029] 2. The present invention is environmentally friendly and can be recovered from the environmental medium by magnets to avoid residues in the environment, thus reducing potential harm to the environment. Using naturally occurring HNTs as a substrate is more environmentally friendly than synthetic materials.

[0030] 3. The present invention is recyclable. The micro-nano robot has good magnetic response characteristics and can be guided by an external magnetic field to facilitate recovery after adsorbing pollutants and realize multiple recycling through pollutant desorption. The high-temperature treatment in a stainless steel autoclave lined with polytetrafluoroethylene ensures the stability and functionality of the material structure, thereby increasing the service life of the micro-nano robot. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of the synthesis of the micro-nano robot of the present invention;

[0032] Figure 2 It is a schematic diagram of the steps of the present invention;

[0033] Figure 3 Schematic diagram of the structure of the micro-nano robot of the present invention;

[0034] Figure 4 This is a flow chart for preparing the micro-nano robot of the present invention. DETAILED DESCRIPTION

[0035] Example 1

[0036] See also Figure 1-Figure 3A micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure, the preparation method comprising the following steps:

[0037] S1. The halloysite nanotubes (HNTs) are subjected to ultrasonic cleaning treatment with water and ethanol, wherein the HNTs have a length of 3-8 μm and a diameter of 50-200 nm.

[0038] S2. Add FeCl3·6H2O, C6H5Na3O7 and NaAc·3H2O to ethylene glycol in sequence and mix under vigorous stirring. The mass ratio of FeCl3·6H2O, C6H5Na3O7 and NaAc·3H2O is 11:4:33.

[0039] FeCl3·6H2O is ferric chloride hexahydrate, an inorganic compound. It is a form of ferric chloride with six crystal water molecules and is a yellow-brown or orange-yellow crystal.

[0040] C6H5Na3O7 is sodium citrate, an organic acid sodium salt, which is a colorless crystal or white crystalline powder.

[0041] NaAc·3H2O is sodium acetate trihydrate, an organic compound, in the form of colorless crystals or white crystalline powder.

[0042] By adding FeCl3·6H2O, C6H5Na3O7 and NaAc·3H2O to ethylene glycol, a uniform suspension can be formed, which is conducive to the subsequent reaction and ensures that the iron ions can be evenly distributed on the surface of HNTs, thereby forming a uniform iron coating. After the iron coating is deposited on the HNTs, it gives the micro-nano robot magnetic response characteristics, enabling it to move in a directional manner under the guidance of an external magnetic field.

[0043] S3. Add HNTs to the mixed solution under continuous stirring, and continue stirring for 1 hour. The mass ratio of HNTs to FeCl3·6H2O, sodium citrate and NaAc·3H2O in S2 is 1:11:4:33, and the stirring time is 1 hour.

[0044] S4. The viscous mixed solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene and reacted at high temperature for 12 hours. The volume of the stainless steel autoclave lined with polytetrafluoroethylene was 100 mL. During the high temperature treatment, the reaction temperature was 200°C and the reaction time was 12 hours.

[0045] S5. Use a permanent magnet to collect the black precipitate in the suspension, and wash it with deionized water and ethanol for multiple times. Dry the washed product in a vacuum to obtain Fe3O4-HNTs. The drying temperature is -60°C and the drying time is 12 h.

[0046] S6. Disperse the dried Fe3O4-HNTs and KMnO4 in deionized water, stir vigorously at room temperature for 20.0 minutes, add HCl, and continue stirring for 30.0 minutes. The mass ratio of Fe3O4-HNTs and KMnO4 is 3:7.

[0047] KMnO4 is potassium permanganate, a strong oxidant. It appears as black-purple or dark green elongated prismatic crystals or particles with a blue metallic luster and no odor. When preparing micro-nano robots, KMnO4 is used to synthesize the MnO2 layer. This layer of material gives the micro-nano robots catalytic activity, enabling them to produce reactive oxygen species in the presence of hydrogen peroxide, which is used to degrade antibiotics in livestock and poultry manure. In addition, MnO2 also helps to adsorb heavy metal ions.

[0048] S7. The mixture is transferred to a stainless steel autoclave lined with polytetrafluoroethylene and subjected to high-temperature treatment for 6 hours. After the treatment, the product is collected by centrifugation, washed with deionized water and ethanol multiple times and dried under vacuum to obtain a MnO2-Fe3O4-HNTs micro-nano robot. The volume of the stainless steel autoclave lined with polytetrafluoroethylene is 50 mL. During the high-temperature treatment, the reaction temperature is 100°C and the reaction time is 6 hours.

[0049] S8. Disperse the MnO2-Fe3O4-HNTs micro-nano robots and g-C3N4 nanosheets in distilled water and shake for 12 hours. The mass ratio of MnO2-Fe3O4-HNTs micro-nano robots and g-C3N4 nanosheets is 4:1.

[0050] S9. Collect the CN-MnO2-Fe3O4-HNTs micro-nano robots by centrifugation, wash them with deionized water for multiple times, and dry them under vacuum. When the micro-nano robots are vacuum dried, the drying temperature is -60°C and the drying time is 12 hours.

[0051] S10. Use scanning electron microscopy, energy dispersive X-ray spectroscopy, UV-visible absorption spectroscopy, photoluminescence emission spectroscopy, fluorescence microscopy images, X-ray diffraction and Fourier transform infrared spectroscopy to detect the characterization of micro-nano robots, and adjust and optimize the composition structure, surface morphology and interface morphology of micro-nano robots to ensure the efficient removal of heavy metals and antibiotics in livestock and poultry manure. When testing the micro-nano robots, the composition structure, surface morphology and interface morphology of the micro-nano robots are detected respectively.

[0052] By precisely controlling the ratio of various materials and using deionized water to form a uniform suspension, uniform deposition of Fe3O4 on HNTs was ensured, thereby improving the uniformity and consistency of the micro-nano robot.

[0053] After depositing Fe3O4 on HNTs, the formed micro-nano robot has good magnetic response characteristics and can guide its movement through an external magnetic field, facilitating subsequent pollutant removal.

[0054] By further depositing a MnO2 layer on the HNTs, the micro-nano robots are endowed with catalytic activity, enabling them to produce reactive oxygen species in the presence of H2O2 for the degradation of antibiotics in livestock and poultry manure, and MnO2 also helps in the adsorption of heavy metal ions.

[0055] By adjusting the pH value of the suspension, optimal conditions for the reaction environment are ensured, promoting the formation of the desired product.

[0056] Multiple washing and drying steps ensure the purity of the final product while also eliminating impurities that may be introduced during the preparation process.

[0057] High temperature treatment in a PTFE-lined stainless steel autoclave ensures the structural stability and functionality of the material.

[0058] In summary, through strict control and optimization, it is ensured that the final prepared micro-nano robot has good magnetic response, catalytic activity and surface characteristics, and is suitable for the removal of heavy metals and antibiotics in livestock and poultry manure.

[0059] Example 2

[0060] A method for detecting the surface characteristics and elemental composition of a micro-nano robot for the removal of heavy metals and antibiotics from livestock and poultry manure:

[0061] Scanning electron microscopy is used to characterize the morphology of micro-nano robots to ensure that they meet the design requirements and have good consistency and uniformity.

[0062] Energy dispersive X-ray spectroscopy was used to analyze the elemental composition of the micro-nano robot and verify the presence of O, C, Mn, Al, Si, N and Fe, thereby confirming whether the micro-nano robot was successfully prepared.

[0063] UV-visible absorption spectroscopy and photoluminescence emission spectroscopy were used to characterize the optical properties of the fluorescent nanosheets.

[0064] Fluorescence microscopy images were used to verify whether the fluorescent nanosheets were evenly integrated on the surface of the micro-nano robot.

[0065] X-ray diffraction was used to confirm the existence of each component in the micro-nano robot.

[0066] Fourier transform infrared spectroscopy is used to identify specific chemical bonds or functional groups of micro-nano robots.

[0067] The adsorption-desorption isotherm test was carried out using the N2 adsorption method to further evaluate the surface characteristics and roughness of the micro-nano robot and determine the pore structure characteristics of the material, including pore size, pore distribution, specific surface area and pore volume.

[0068] The magnetization curves were used to demonstrate the magnetic response characteristics of the micro-nano robot, including rapid separation and collection capabilities.

[0069] X-ray photoelectron spectroscopy was used to analyze the elemental valence state of the micro-nano robot, confirming the presence of O, C, Mn, Al, Si, N and Fe elements, as well as Fe 3+ and Fe 2+ and Mn 4+ existence.

[0070] Example 3

[0071] A method for detecting the migration performance of a micro-nano machine for removing heavy metals and antibiotics from livestock and poultry manure comprises the following steps:

[0072] The movement performance of the micro-nano robot was tested under a microscope. When the micro-nano robot was placed in a solution containing H2O2, the MnO2 modified on the inner surface of the tube catalyzed the decomposition of H2O2 to produce O2 bubbles, and the bubbles continuously ejected from one end of the microtube pushed the micro-nano robot to the other side.

[0073] The tracking trajectory of the micro-nano robot within 2 seconds was tested in 0.5, 1.0, 1.5 and 2.0wt% H2O2, and the average speed was calculated, showing a positive correlation between the moving distance and average speed and the H2O2 concentration.

[0074] The motion trajectory was recorded under a 50x objective lens, and the tracking trajectory and average speed were obtained from the recorded video using NIS-Elements AR 3.2 software.

[0075] In order to further verify the feasibility of micro-nano robots moving in microchannels.

[0076] A chip with a regular microchannel structure (500 microns wide) was used as an experimental platform to verify whether the micro-nano robot could move in a directed manner between the two chambers of the microchip under the action of a magnetic field.

[0077] To further simulate the condition of no magnetic field, one chamber contained H2O2 solution and the other chamber contained pure water environment, to observe whether the micro-nano robot could achieve traversal in the microchannel through effective self-propulsion and strong bubble generation.

[0078] Furthermore, in order to simulate the complex and changeable channel structure in the real environment, the migration of micro-nano robots in heterogeneous porous environments was studied. A columnar device filled with sandy quartz was used to conduct a comparative study of static micro-nano robots and self-propelled micro-nano robots. The prepared micro-nano robots were black and their positions could be directly observed from the color. The static micro-nano robots were placed in water, and the self-propelled micro-nano robots were placed in hydrogen peroxide.

[0079] Furthermore, in order to prove the migration caused by the micro-nano robot in the absence of water flow, the micro-nano robot was placed at the bottom of the column, the water outlet was closed, and it was observed whether the micro-nano robot could overcome gravity and move upward in the presence of hydrogen peroxide in the absence of water flow.

[0080] Since the speed of the micro-nano robot is positively correlated with the concentration of hydrogen peroxide, the effect of hydrogen peroxide concentration on the migration of the micro-nano robot in the column was further tested.

[0081] The hydrogen peroxide concentration was adjusted from 1.0 to 3.0wt%, and the microrobots passing through the column were collected and weighed for quantitative analysis. The ratio of the mass of the microrobots recovered from the beaker to the mass of the microrobots initially added was used to evaluate the migration efficiency at different fuel concentrations.

[0082] Example 4

[0083] A method for detecting the migration of a micro-nano machine in livestock and poultry manure for removing heavy metals and antibiotics in livestock and poultry manure comprises the following steps:

[0084] A culture dish filled with livestock and poultry manure was used to study the horizontal migration of the micro-nano robot. The micro-nano robot was placed in the center of the culture dish, and then 1 mL of water or 3.0 wt% H2O2 was added dropwise. During this period, the parallel migration of the micro-nano robot was observed by fluorescence under ultraviolet light.

[0085] Subsequently, a livestock and poultry manure-filled column with three sampling points was used to verify the vertical migration ability of the micro-nano robot. The migration of the micro-nano robot was evaluated by the change in the fluorescence intensity of the eluate collected at the three sampling points. The original fluorescence intensity of sampling point 1 was defined as 100%, and the fluorescence intensity of the three sampling points was determined at different time intervals. In addition, the vertical migration was further verified by evaluating the number ratio of the micro-nano robots in the eluate collected at the three sampling points.

[0086] Example 5

[0087] A method for heavy metal removal and antibiotic degradation detection using a micro-nano machine for removing heavy metals and antibiotics from livestock and poultry manure comprises the following steps:

[0088] 3 mg of the micro-nano robot was added to 10 mL of livestock and poultry manure solution, which contained 1 ppm of Cu 2+ , Pb 2+ 、Cd 2 + 5 wt% H2O2 was added to start the reaction, and after the microrobot was allowed to swim for 7 and 15 minutes, the concentrations of the three heavy metals were determined by square wave voltammetry at two time intervals using a mercury-coated glassy carbon electrode as the working electrode. Before the measurement, H2O2 was removed by adding an excess of 1 M sodium bisulfate solution to avoid interference with the electrochemical signal.

[0089] 3 mg of the micro-nano robot was added to 10 mL of livestock and poultry manure solution containing 50 ppm of tetracycline or other antibiotics, 1 mM PMS was added as an activator, and 5 wt% H2O2 was added to start the reaction. During the reaction, liquid samples were taken out regularly and their absorbance at 358 nm was immediately measured using a UV-vis spectrophotometer.

[0090] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure, characterized in that: The preparation method comprises the following steps: S1, subjecting the halloysite nanotubes (HNTs) to ultrasonic cleaning with water and ethanol; S2, add FeCl3·6H2O, C6H5Na3O7 and NaAc·3H2O to ethylene glycol in sequence and mix under vigorous stirring; S3, adding HNTs to the mixed solution under continuous stirring, and continuing stirring for 1 hour; S4, transferring the viscous mixed solution to a stainless steel autoclave lined with polytetrafluoroethylene and reacting at high temperature for 12 hours; S5, using a permanent magnet to collect the black precipitate in the suspension, and washing it with deionized water and ethanol for multiple times, and drying the washed product in a vacuum to obtain Fe3O4-HNTs; S6, disperse the dried Fe3O4-HNTs and KMnO4 in deionized water, stir vigorously at room temperature for 20.0 minutes, add HCl, and continue stirring for 30.0 minutes; S7, transferring the mixture into a stainless steel autoclave lined with polytetrafluoroethylene and subjecting it to high temperature treatment for 6 hours, collecting the product by centrifugation after the treatment, washing it with deionized water and ethanol for multiple times and drying it under vacuum to obtain a MnO2-Fe3O4-HNTs micro-nano robot; S8, disperse the MnO2-Fe3O4-HNTs micro-nano robots and g-C3N4 nanosheets in distilled water and shake for 12 hours; S9, collecting the CN-MnO2-Fe3O4-HNTs micro-nano robots by centrifugation, washing them with deionized water for several times, and drying them under vacuum; S10. Use scanning electron microscopy, energy dispersive X-ray spectroscopy, UV-visible absorption spectroscopy, photoluminescence emission spectroscopy, fluorescence microscopy images, X-ray diffraction and Fourier transform infrared spectroscopy to detect the characterization of the micro-nano robot, and adjust and optimize the composition structure, surface morphology and interface morphology of the micro-nano robot to ensure the efficient removal of heavy metals and antibiotics in livestock and poultry manure.

2. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: The HNTs in S1 have a length of 3-8 μm and a diameter of 50-200 nm.

3. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: The mass ratio of FeCl3·6H2O, C6H5Na3O7 and NaAc·3H2O in the S2 is 11:4:

33.

4. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: The mass ratio of the HNTs in the S3 to the FeCl3·6H2O, sodium citrate and NaAc·3H2O in the S2 is 1:11:4:33, and the stirring time is 1 h.

5. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: The volume of the polytetrafluoroethylene-lined stainless steel high-pressure reactor in S4 is 100 mL; during high-temperature treatment, the reaction temperature is 200° C. and the reaction time is 12 h.

6. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: The drying temperature in S5 is -60°C and the drying time is 12 hours.

7. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: The mass ratio of Fe3O4-HNTs and KMnO4 in the S6 is 3:

7.

8. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: The volume of the polytetrafluoroethylene-lined stainless steel high-pressure reactor in S7 is 50 mL; when performing high-temperature treatment, the reaction temperature is 100° C. and the reaction time is 6 h.

9. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: The mass ratio of the MnO2-Fe3O4-HNTs micro-nano robots and g-C3N4 nanosheets in the S8 is 4:

1.

10. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: When the micro-nano robot in S9 performs vacuum drying, the drying temperature is -60°C and the drying time is 12 hours.

11. The micro-nano robot for removing heavy metals and antibiotics from livestock and poultry manure according to claim 1, characterized in that: When the micro-nano robot is detected in S10, the component structure, surface morphology and interface morphology of the micro-nano robot are detected respectively.

Images