Separate collection structure for liposoluble and hydrosoluble pesticides and method for its preparation

Abstract

The present application relates to a separation and collection structure for fat-soluble and water-soluble pesticides and a preparation method thereof, the structure being a corrosion-resistant porous foam structure with an inner cavity, the inner and outer surfaces of which are plated with a layer of noble metal micro-nanoparticles; when the separation and collection structure is used as an oil collector, a triangular array is processed on the layer of noble metal micro-nanoparticles on the outer surface of the structure by femtosecond laser, the structure has hydrophilic properties, and the inner surface of the structure has hydrophobic properties; when the separation and collection structure is used as a water collector, a triangular array is processed on the layer of noble metal micro-nanoparticles on the inner surface of the structure by femtosecond laser; the triangular array region of the inner surface of the structure has hydrophilic properties, and the outer surface of the structure has hydrophobic properties; the triangular array region is used to guide the separated liquid droplets to move in a directional manner towards the sharp corners of the triangular array region and to be collected in the inner cavity of the structure. The present application can realize efficient separation of oil and water, and the triangular hydrophilic region can induce microdroplets to move and converge in a specific direction, thereby realizing smooth collection.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of oil-water separation, and particularly relates to a separation and collection structure for liposoluble and water-soluble pesticides and a preparation method thereof. BACKGROUND

[0002] Pesticides can prevent or reduce crop pests and diseases to a certain extent, but if pesticides are used excessively or discharged unreasonably, water quality will be polluted, thereby endangering human life and health. Pesticides can be divided into liposoluble and water-soluble pesticides according to solubility, and it is difficult to extract and degrade the two types of pesticides simultaneously due to the different properties of the two types of pesticides. It is a scientific method of pesticide separation and treatment to put oil into water to dissolve liposoluble pesticides in oil, thereby separating liposoluble and water-soluble pesticides and then treating them separately. However, the current separation of oil containing certain components from water has the problems of complicated pretreatment steps, difficulty in separating oil from water, low separation rate, high cost, and unsuitability for large-area contaminated water. It is often an effective means to separate liquids of different densities by using the surface micro-nano structure of the material. When the wettability of the surfaces on both sides of the material is different, the liquid will tend to flow from the hydrophobic side to the hydrophilic side. According to this principle, oil and water can be separated. However, the existing technology has the problems of easy separation and difficult collection, and the collected pesticide components often cannot be detected in situ and need to be further detected and treated. SUMMARY

[0003] The present application aims to overcome the shortcomings of the prior art and provide a separation and collection structure for liposoluble and water-soluble pesticides and a preparation method thereof.

[0004] One of the above-mentioned purposes of the present application is achieved by the following technical solution:

[0005] A separation and collection structure for liposoluble and water-soluble pesticides, the separation and collection structure being an anticorrosive porous foam structure having an inner cavity, the inner surface and the outer surface of the structure being plated with a layer of noble metal micro-nano particles;

[0006] When the separation and collection structure is used as an oil collector, a triangular array is processed on the layer of noble metal micro-nano particles on the outer surface of the structure by femtosecond laser; the triangular array region of the outer surface of the structure has hydrophilic properties and is a hydrophilic region, and the inner surface of the structure has hydrophobic properties and is a hydrophobic side;

[0007] When the separation and collection structure is used as a water collector, a triangular array is processed on the layer of noble metal micro-nano particles on the inner surface of the structure by femtosecond laser; the triangular array region of the inner surface of the structure has hydrophilic properties and is a hydrophilic region, and the outer surface of the structure has hydrophobic properties and is a hydrophobic side;

[0008] The triangular array area is used for guiding the separated liquid drops to realize directional movement towards the sharp corner of the triangle and to gather in the inner cavity of the structure.

[0009] Moreover, the material of the corrosion-resistant porous foam is metal organic framework, foam metal or porous polymer.

[0010] Moreover, the thickness of the corrosion-resistant porous foam in the inner-outer direction is 0.3-4 mm.

[0011] Moreover, the electroplated noble metal nanoparticles are gold, silver, platinum and alloy particles thereof.

[0012] Moreover, the corrosion-resistant porous foam has a barrel shape, a funnel shape or a cuboid shape.

[0013] Moreover, the side length of the triangular array processed by the femtosecond laser is less than 100 microns.

[0014] The second of the above-mentioned purposes of the application is realized by the following technical solution:

[0015] A preparation method based on the structure for separating fat-soluble and water-soluble pesticides, characterized by comprising the following steps:

[0016] Step 1: The porous foam material is placed in an electrolytic cell solution containing noble metal ions for electroplating treatment, so that the two surfaces of the material are electroplated with noble metal particles to form a noble metal particle layer;

[0017] Step 2: The femtosecond laser spot is shaped into a triangle by using an air space shaping system, and the foam material is punched on one side surface after step 1, and the computer is controlled to process the triangular array on the side surface of the material according to the set shape;

[0018] Step 3: The processed porous foam material is shaped into a closed three-dimensional separation collector with an inner cavity.

[0019] Moreover, in step 1, the electroplating time is 5-30 s, and the current range is 0.05-0.3 A.

[0020] Moreover, in step 2, the laser flux used for laser punching is 1.0-2.0 J / cm 2 .

[0021] The application has the advantages and positive effects that:

[0022] 1. The application is a multifunctional anti-corrosion structure for separating and collecting liposoluble and water-soluble pesticides, which integrates pesticide separation, collection and detection. The inner surface of the structure contains a large number of noble metal micro-nano structures with SERS detection capability. According to the needs of collecting oil or water, a triangular array of a specified shape is machined on the outer surface or the inner surface by femtosecond laser processing, so that the triangular array area is hydrophilic, and the unprocessed side is hydrophobic. This structure can efficiently separate oil and water, and the triangular hydrophilic area can induce microdroplets to move and converge in a specific direction, achieving smooth collection.

[0023] 2. The application is a preparation method for the separation structure of liposoluble and water-soluble pesticides. By surface electroplating of noble metal particles and spatial shaping of femtosecond laser array dot processing, the two sides of the anti-corrosion foam material can be manufactured with opposite wettability. The flexibility of the laser allows more arrangement of the hydrophilic triangular area, and the processing method is fast and convenient.

[0024] 3. The application range of the application of the separation structure of liposoluble and water-soluble pesticides and its preparation method is mainly the separation process of pesticides with different solubilities in large-area water. By bending and shaping the processed flexible material, oil-water separation can be flexibly carried out in water contaminated by various pesticides, and liposoluble pesticides dissolved in oil can be separated from water-soluble pesticides dissolved in water, thereby facilitating subsequent separate degradation treatment. It has environmental protection and practicality. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The flowchart of the preparation method of the structure for separating liposoluble and water-soluble pesticides in Example 1 of the application is as follows:

[0026] In the figure, (a) is a flexible anti-corrosion foam material to be processed; (b) is a material electroplating treatment, so that noble metal micro-nano particles are electroplated on the skeleton of the foam material; (c) is spatial shaping femtosecond laser dot processing on the lower surface of the material, the processing shape is a triangle, and the triangle arrangement is controlled by a computer; (d) is the processed structure is rolled up and shaped, for example, shaped into a barrel shape, which can be applied to the rapid separation process of oil and water containing pesticides.

[0027] Figure 2 The femtosecond laser processing system diagram for preparing the triangular hydrophilic area in the example of the application is as follows:

[0028] 1 - femtosecond laser; 2 - grating; 3 - attenuator; 4 - optical shutter; 5 - spatial light modulator; 6 - mirror; 7 - plano-convex lens; 8 - plano-convex lens; 9 - mirror; 10 - lens; 11 - focusing lens; 12 - substrate to be processed; 13 - six-dimensional translation stage; 14 - computer;

[0029] Figure 3Two kinds of triangle array forms machined by femtosecond laser for the embodiment of the present application are shown in the schematic diagram.

[0030] Figure 4 The schematic diagram of the structure machined by the embodiment of the present application applied to the oil-water separation process of fat-soluble pesticides and water-soluble pesticides is shown. DETAILED DESCRIPTION

[0031] The structure of the present application is further described below in combination with the drawings and by examples. It should be noted that the examples are descriptive rather than limiting.

[0032] A structure for separating fat-soluble and water-soluble pesticides and a method for preparing the same are described in Figures 1-4 The invention points of the structure are as follows:

[0033] Step one: The flexible foam material is placed in an electrolytic cell solution containing noble metal ions for electroplating treatment, so that the two surfaces of the material are electroplated with noble metal particles;

[0034] Step two: The femtosecond laser spot is shaped into a triangle by using a spatial shaping system, and the foam material is punched on one side surface after the step one processing, so that the material is processed into a variety of arrangement modes of triangle array on the side surface by computer control;

[0035] Step three: The processed flexible material is shaped into a closed barrel, funnel or cuboid structure form of three-dimensional separation collector, which can be used to collect oil containing fat-soluble pesticides or water containing water-soluble pesticides in a large area of pesticide contaminated water.

[0036] The surface of the foam material is electroplated to produce a large number of micro-nano composite particles on the skeleton. These noble metal micro-nano particles not only make the surface of the foam material more hydrophobic, but also provide "hot spots" for realizing surface Raman enhancement detection. Then the femtosecond laser is punched on one side surface of the material for spatial shaping, and the shaped spot shape is a variety of triangles. The inside of the triangle area processed by the femtosecond laser is hydrophilic. Through the above processing steps, a hydrophilic-hydrophobic liquid directional transport structure can be constructed, which realizes oil-water separation while the liquid droplets move along a specific direction of the triangle and gather, thereby realizing oil-water separation and directional collection and convergence.

[0037] In the separation of liposoluble pesticides and water-soluble pesticides in water polluted by multiple pesticides, first, oil dissolving liposoluble pesticides is added to the water, and then the separation collector manufactured by the technical solution is put into the water, and when collecting oil, the side of the hydrophilic triangular area is outward, and when collecting water, the side of the hydrophilic triangular area is inward. By dragging and rolling the separation collector, oil and water can be efficiently separated, and an oil film containing liposoluble pesticides can be collected. After the oil film is collected, the large amount of noble metal micro-nano structures attached to the hydrophobic surface inside the collector can be used for surface Raman detection of the substances contained in the oil droplets, so as to obtain the composition of the liposoluble pesticides.

[0038] Further, in order to meet the need of transporting droplets from the pores in the material, the thickness of the corrosion-resistant foam material ranges from 0.3mm to 4mm. The noble metal plated in the electroplating process described in step one can be selected from gold, silver, platinum and their alloys. By controlling the series of parameters during electroplating, the noble metal particles are deposited on the surface of the foam material skeleton without blocking the pores of the skeleton. The electroplating time can be selected as 5-30s, and the current range can be selected as 0.05-0.3A. The electroplating can flexibly control the particle morphology of the deposited noble metal, so that the surface presents a hydrophobic state, and provides an effective "hot spot" for detecting pesticide components.

[0039] The spatial shaping femtosecond laser processing process described in step two requires the use of a spatial shaper to shape the originally circular femtosecond laser Gaussian spot into a triangle. Through computer control, the triangular spot can be changed into various different right-angled, acute-angled and obtuse-angled triangles. By controlling the laser energy and scanning speed during laser scanning, the laser flux is ensured to be 1.0-2.0J / cm 2 Dot processing is performed on one side surface of the material processed in step one, and the dot spacing during laser processing can be controlled by computer control to control the distribution density of the triangles.

[0040] In the processed triangular area, due to the large laser flux, the skeleton of the foam material presents a micro-nano composite structure after ablation, the pores between the skeletons become larger, and present a hydrophilic state.

[0041] The electroplating device for realizing the above method comprises an electrolytic cell, an electrolyte containing noble metal ions, a cathode (corrosion-resistant foam material to be electroplated), an anode, a digital source meter, and an electric wire.

[0042] The spatial shaping femtosecond laser processing device for realizing the above method comprises a femtosecond laser, a grating, an attenuation sheet, a spatial light modulator, an optical shutter, a mirror, a focusing lens and a six-axis translation stage. After femtosecond laser pulses are emitted from the femtosecond laser 1, the femtosecond laser pulses pass through the grating 2 and the attenuation sheet 3 in sequence, and then the optical shutter 4 is used to control the opening and closing of the laser. Subsequently, the laser enters the spatial light modulator 5 controlled by a computer, the originally circular light spot can be shaped, and the triangular light spot topography is shaped by using a phase map. The shaped light is reflected from the spatial light modulator to the mirror 6, introduced into the plano-convex lens group composed of the first plano-convex lens 7 and the second plano-convex lens 8 via the mirror, and then the light enters the lens 10 and the focusing lens 11 via the mirror 9 to irradiate the surface of the substrate 12 to be processed, and the substrate 12 to be processed is placed on the six-dimensional translation stage 13. The movement of the six-dimensional translation stage 13 is controlled by the computer 14, so as to drive the movement of the material above, so that the femtosecond laser which has been spatially shaped by the spatial light modulator can make triangular dot arrays on the surface of the material.

[0043] Embodiment:

[0044] A structure for separating fat-soluble and water-soluble pesticides and a preparation method thereof are disclosed, taking a foamed aluminum material with a thickness of 0.5 mm as an example. The manufacturing steps are as follows:

[0045] Step one: place the material in an electrolytic cell and connect it to the cathode for electroplating treatment. In this process, the electroplated noble metal is gold, the electrolyte is a gold chloride solution, and the electroplating time is controlled to be 20 s and the current is controlled to be 0.1 A. The processing process is as shown in Figure 1 (b).

[0046] Step two: place the material with gold micro-nanoparticles electroplated on both sides on a femtosecond laser processing translation stage, and punch a triangular array on one surface of the material. The processing process is as shown in Figure 1 (c).

[0047] In the present application, the laser center wavelength of the femtosecond laser 1 is 800 nm, the pulse width is 50 fs, the maximum repetition frequency is 1 KHz, and the light intensity distribution is Gaussian. The processing optical path system diagram is as shown in Figure 2 . 2 .

[0048] Step three: place the flexible material with the unprocessed side inward and the laser-processed side outward to form a closed barrel shape, which can be used to collect oil containing fat-soluble pesticides in a large area of pesticide-contaminated water, as shown in Figure 1 (d).

[0049] Several typical area shapes for separating fat-soluble and water-soluble pesticides are processed by the femtosecond laser processing process shown in the examples.

[0050] The triangular micro-area can guide the droplets to move more easily towards the tip when collecting the droplets, so as to achieve the purpose of gathering more micro-droplets into larger droplets. Figure 3 a With Figure 3 b shows two typical schematic diagrams of laser processing triangular array guiding droplet gathering, wherein each triangle is a region of femtosecond laser spot ablation of spatial shaping.

[0051] The specific scheme of separating and collecting fat-soluble and water-soluble pesticides in the pesticide-contaminated water area by the oil-water separation device manufactured in Example 1 is shown in Figure 4 FIG.

[0052] In this embodiment, the purpose is to separate the fat-soluble pesticides in the pesticide-contaminated water, so the femtosecond laser processing is outward, and the material is made into a closed gasoline barrel-shaped separation collector. Before collection, fat-soluble pesticides are dissolved in oil film by adding oil that can dissolve fat-soluble pesticides into the contaminated water area. The separation collector is bound with a rope outside, and the separation collector is moved on the water surface by dragging the rope. During the process, the oil film penetrates from the outside to the inside through the internal driving force caused by the hydrophilic-hydrophobic interface of the material. Since the triangular hydrophilic area guides the movement of the droplets, the oil micro-droplets that penetrate into the inside tend to move in a fixed direction and gather, and are more easily detached from the surface of the material, thereby improving the oil-water separation rate and the collection efficiency. By this method, fat-soluble pesticides can be more efficiently separated from water-soluble pesticides, and subsequent separate degradation is facilitated. At the same time, the inner wall of the material has a large number of noble metal micro-nano composite structures due to electroplating, so the collected oil can be directly poured out, and then a piece of the inner wall can be cut and taken as a detection substrate. After adding the collected oil, surface-enhanced Raman scattering detection is performed, so that the composition of the collected oil content can be detected.

[0053] Although the embodiments of the present application and the drawings are disclosed for the purpose of illustration, those skilled in the art can understand that various alternatives, changes and modifications are possible without departing from the spirit of the present application and the appended claims, therefore, the scope of the present application is not limited to the disclosed content of the embodiments and the drawings.

Claims

1. A method for preparing a separate collection structure for a fat-soluble and water-soluble pesticide, characterized by: The separation and collection structure is a corrosion-resistant porous foam structure with an inner cavity, and the inner and outer surfaces of the structure are plated with a layer of noble metal micro-nanoparticles; When the separation and collection structure is used as an oil collector, a triangular array is processed on the noble metal micro-nanoparticle layer on the outer surface of the structure by femtosecond laser; the outer surface triangular array region of the structure has hydrophilic properties and is a hydrophilic region, and the inner surface of the structure has hydrophobic properties and is a hydrophobic side; When the separation and collection structure is used as a water collector, a triangular array is processed on the noble metal micro-nanoparticle layer on the inner surface of the structure by femtosecond laser; the inner surface triangular array region of the structure has hydrophilic properties and is a hydrophilic region, and the outer surface of the structure has hydrophobic properties and is a hydrophobic side; The triangular array region is used to guide the directional movement of separated droplets towards the sharp corners of the triangle and collect them in the inner cavity of the structure; The separation and collection structure is placed in water, and one side of the hydrophilic triangular region is outward when collecting oil, and vice versa when collecting water; The preparation method comprises the following steps: Step 1: Place the porous foam material in an electrolytic cell solution containing noble metal ions for electroplating treatment, so that both surfaces of the material are plated with noble metal particles to form a layer of noble metal particles; Step 2: Use an air space shaping system to shape the femtosecond laser spot into a triangle, and dot the side surface of the foam material processed in step 1, and use a computer to control the processing of the triangular array on the side surface of the material according to the set shape; Step 3: Shape the processed porous foam material into a closed structure with an inner cavity.

2. The method for preparing a separate collection structure for a fat-soluble and water-soluble agricultural chemical according to claim 1, characterized by: The material of the corrosion-resistant porous foam is metal organic framework, foam metal or porous polymer.

3. The method for preparing a separate collection structure for a fat-soluble and water-soluble agricultural chemical according to claim 1, characterized by: The thickness of the corrosion-resistant porous foam in the inner and outer directions is 0.3 mm-4 mm.

4. The method for preparing a separate collection structure for a fat-soluble and water-soluble agricultural chemical according to claim 1, characterized by: The electroplated noble metal nanoparticles are gold, silver, platinum and alloy particles.

5. The method for preparing a separate collection structure for a fat-soluble and water-soluble agricultural chemical according to claim 1, characterized by: The shape of the corrosion-resistant porous foam is barrel-shaped, funnel-shaped or cuboid-shaped.

6. The method for preparing a separate collection structure for a fat-soluble and water-soluble agricultural chemical according to claim 1, characterized by: The edge length of the triangular array processed by femtosecond laser is less than one hundred microns.

7. The method for preparing a separate collection structure of a fat-soluble and water-soluble agricultural chemical according to claim 1, characterized by: In step 1, the electroplating time is 5-30 s, and the current range is 0.05-0.3 A.

8. The method for preparing a separate collection structure of a fat-soluble and water-soluble agricultural chemical according to claim 1, characterized by: In step 2, the laser fluence used for the laser dotting is 1.0-2.0 J / cm 2 .

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