A method for preparing a photo-thermal anti-adhesion sponge by liquid marble pore-making-in-situ surface-embedding and a sponge prepared thereby

Abstract

The application belongs to the technical field of environment-friendly functional material preparation, and aims at overcoming the defects of the existing oil-absorbing sponge preparation, such as uncontrollable sponge aperture, poor durability and high price. The application provides a method for preparing a photothermal anti-adhesion sponge by liquid marble pore-forming and in-situ surface embedding and the prepared sponge. Solid hydrophobic nanoparticles with photothermal effect and liquid form a solid-liquid hybrid liquid marble through a rolling method, PDMS and a curing agent are mixed to form a precursor liquid, isopropyl alcohol is added to change the viscosity of the precursor liquid, the liquid marble is transferred to the precursor liquid, the pore-forming is completed by controlling the solidification temperature to make the liquid marble break, and the solid nanomaterial is embedded in the precursor, so that the photothermal anti-adhesion sponge with adjustable pore structure and recyclability is obtained by the synergistic effect of the photothermal effect and the surface anti-adhesion chemical modification. The prepared photothermal sponge not only has the oil absorption capacity of commercial sponge, but also has good recyclability, and has a wide development prospect in the direction of oil-water separation.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of environmental-friendly functional material preparation, and particularly relates to a method for preparing a photothermal anti-adhesion sponge by liquid bead pore-forming and in-situ surface embedding and the sponge prepared by the method. BACKGROUND

[0002] Crude oil, as a vital natural resource, has greatly improved the quality of human life. However, whether it is an accidental offshore oil spill or a perennial ship pollution, it has caused great impact and threat to the marine environment. In recent decades, researchers have developed various types of adsorbents for treating oil-containing wastewater. However, ordinary adsorbents at room temperature are only effective for low-viscosity oil stains, and the adsorption efficiency for high-viscosity oil stains (such as crude oil) is very low. On the other hand, to cope with the decreasing reserves of light crude oil, the demand for heavy crude oil exploitation by humans will gradually increase in the future.

[0003] Due to the high viscosity of crude oil and the non-flowing nature of heavy crude oil, there are additional problems in exploitation and transportation. According to the temperature sensitivity of crude oil, photothermal, magnetothermal, electrothermal and other thermal effects have been widely studied and applied, so nano materials with thermal effects are integrated with ordinary adsorbents to change the rheological properties of crude oil by using the thermal effect of adsorbents, thereby greatly improving the adsorption rate. As a renewable and clean source of energy, sunlight has received widespread attention from the academic and industrial communities.

[0004] The application number is 202110636341.8, the invention name is a super-hydrophobic photothermal adsorption material capable of treating viscous crude oil and a preparation method thereof, and the publication date is August 31, 2021. The invention discloses a super-hydrophobic photothermal adsorption material capable of treating viscous crude oil and a preparation method thereof. The method uses aniline as a monomer, ammonium persulfate as an oxidizing agent, doped acid as perfluorooctanoic acid, uses PDMS as a bonding agent, uses porous melamine sponge as a substrate, and uses in-situ chemical oxidation polymerization and PDMS immersion method to synthesize a polyaniline composite material with super-hydrophobic photothermal conversion performance. However, this method uses porous sponge as a substrate, and the pore structure cannot be controlled, which limits the separation efficiency and flux to a certain extent.

[0005] The application number is 202110254424.0, the invention name is a super-hydrophobic cotton material with photothermal effect and its preparation method and application, and the publication date is 2021.07.06. The patent discloses a super-hydrophobic cotton material with photothermal effect and its preparation method and application. The method is to modify the multi-hydroxyl carbon nanotube (CNT) to be super-hydrophobic, then load TEOS and HDTMS on the CNT, and after a series of reactions such as hydrolysis and condensation, the super-hydrophobic nanoparticles are obtained after drying. The super-hydrophobic cotton material with photothermal effect is obtained by using the excellent adhesion of PDMS to adhere the nanoparticles on the cotton material. However, this method has the problem that the carbon nanotube is not firmly combined with the cotton material, resulting in poor durability of the porous material.

[0006] The application number is 201910174010.X, the invention name is a preparation method of an oil-water separation material with photothermal responsiveness, and the publication date is 2020.06.30. The patent discloses a preparation method of an oil-water separation material with photothermal responsiveness, which comprises the following steps: 1) synthesizing a copolymer of acrylamide and acrylonitrile; 2) preparing reduced graphene oxide; 3) mixing the copolymer and the reduced graphene oxide into a solvent to obtain a spinning solution, and preparing a finished product by electrostatic spinning. This method uses electrostatic spinning method, and the preparation cost is high. SUMMARY

[0007] In order to overcome the problems of complex process, poor durability, uncontrollable pore structure, limited separation efficiency and flux, and poor crude oil adhesion in the process of preparing the existing oil absorption sponge, a method for preparing a photothermal anti-adhesion sponge by liquid bead pore forming-in-situ surface embedding and the prepared sponge are provided. The method for preparing a photothermal anti-adhesion sponge by liquid bead pore forming-in-situ surface embedding is simple, easy to operate and pollution-free. The obtained photothermal anti-adhesion sponge has adjustable pore size, stable internal structure, high pressure resistance and can be reused. And the in-situ embedding method can firmly bind the modifiers to the sponge.

[0008] The method for preparing a photothermal anti-adhesion sponge by liquid bead pore forming-in-situ surface embedding is realized by the following technical scheme: solid-hydrophobic nanoparticles with photothermal effect and liquid are formed into solid-liquid hybrid liquid beads by rolling method, PDMS and curing agent are mixed to obtain a precursor liquid, isopropyl alcohol is added to change the viscosity of the precursor liquid, the liquid beads are transferred to the precursor liquid, and then the solidification temperature is controlled to make the liquid beads break, so as to complete the pore forming, and the released solid nanomaterial is embedded in the precursor body. By using the synergistic effect of photothermal effect and surface anti-adhesion chemical modification, a photothermal anti-adhesion sponge Ag / PDMS sponge with adjustable pore structure and reusability is obtained.

[0009] The solid hydrophobic nanoparticles are one of silver, polypyrrole and graphene or a mixture of any two of them in any ratio; and the liquid is water, ethylene glycol or a sodium alginate aqueous solution.

[0010] The specific method is:

[0011] (1) Preparation of liquid beads: the nanoparticles are hydrophobized, then the hydrophobic nanoparticles are laid on a substrate, a micro-syringe is used to suck the liquid, the liquid is dropped on the substrate covered with the hydrophobic nanoparticles, and the liquid beads are formed by rolling the hydrophobic nanoparticles to self-wrap the liquid drops;

[0012] (2) Preparation of precursor liquid: PDMS and curing agent are mixed at a mass ratio of 1:0.1, isopropyl alcohol is added at a volume concentration of 20-30%, and the mixture is mixed in a vortex mixer for 2 min, and then vacuumed by a 2 Pa vacuum pump for 5 min to obtain the precursor liquid;

[0013] (3) Preparation of photo-thermal anti-adhesion sponge: 1 g of the precursor liquid prepared in step (2) is dropped on a glass sheet, and the liquid beads prepared in step (1) are transferred to the precursor liquid, and after the liquid beads are settled for 3-5 min, the glass sheet is placed in a constant-temperature oven at 30-90°C for 2-3 h to obtain the photo-thermal anti-adhesion sponge.

[0014] The specific method for hydrophobizing the nanoparticles in step (1) is as follows: 1 g of nanoparticles is mixed with 254 μL of octadecyltrichlorosilane and 15 ml of n-hexane, ultrasonically treated for 20 min, then left to stand for 2 h, centrifuged at 8000 r / min, and vacuum dried at 50°C for 2 h to obtain the hydrophobic nanoparticles; the mass / volume ratio of the hydrophobic nanoparticles to the liquid is 1:1-8 g / μL; and the rolling frequency is 10-20 times.

[0015] Further, the rolling frequency is 10 times, 15 times or 20 times.

[0016] In step (1), the liquid is a sodium alginate aqueous solution with a concentration of 2 wt%, the nanoparticles are polypyrrole, and the mass / volume ratio of the hydrophobic nanoparticles to the liquid is 1:5 g / μL.

[0017] In step (2), the mass ratio of PDMS to isopropyl alcohol is 1:0.05.

[0018] In step (3), the liquid beads are transferred to the precursor liquid according to a mass ratio of PDMS to the liquid beads of 0.9-1.2.

[0019] The application also provides a photo-thermal anti-adhesion sponge obtained by the above preparation method.

[0020] The application also provides application of the photothermal anti-adhesion sponge in adsorbing and removing high-viscosity and anti-flow heavy oil pollution.

[0021] The curing agent used in the application is a curing agent matched with the commonly commercially available Dow Corning Sylgard 184 PDMS.

[0022] Compared with the prior art, the liquid beads of the application are solid-liquid hybrid materials with certain mechanical strength formed by wrapping solid nanomaterials on the surface of liquid droplets, and a large amount of gas is loaded in the interior, and through heating, the gas can break the liquid beads and be released to the polymer precursor to complete the pore forming, and it is found through experimental verification that it is feasible to balance the mechanical strength and mechanical elasticity of the sponge material by foaming and pore forming to embed the nanomaterials on the surface of the sponge skeleton. Embedding the nanomaterials in the interior of the sponge can firmly embed the modifiers on the surface of the PDMS, and enhance the durability. By using the synergistic effect of the photo-induced heating effect and the surface anti-adhesion chemical modification, the Ag / PDMS sponge can be used for cleaning high-viscosity and anti-flow heavy oil pollution. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The particle size distribution and actual object diagram of the PPy liquid beads prepared by the rolling method; in the diagram: a is the actual object diagram of the PPy liquid beads; b is the particle size distribution diagram of the PPy liquid beads;

[0024] Figure 2 The particle size distribution and actual object diagram of the Ag liquid beads prepared by the rolling method; in the diagram: a is the actual object diagram; b is the particle size distribution diagram;

[0025] Figure 3 The liquid beads with particle sizes of 1-2 mm and 2-3 mm prepared in Example 1 embedded in PDMS;

[0026] Figure 4 The elasticity and mechanical properties of PPy / PDMS sponges with different PDMS:LM;

[0027] Figure 5 The influence of different PDMS:LM on the elasticity of Ag / PDMS sponges and the influence of the elastic recovery time;

[0028] Figure 6 The micro-morphologies of the PDMS sponge and the PPy / PDMS sponge; in the diagram: (a1), (a2) are the micro-morphologies of the PDMS sponge; (b1), (b2) are the micro-morphologies of the PPy / PDMS sponge;

[0029] Figure 7 The water contact angle test and the underwater oil contact angle test of the PPy / PDMS sponge;

[0030] Figure 8a. Adsorption capacity of PPy / PDMS sponge for different oils; b. Test chart of PPy / PDMS sponge adsorbing heat conducting oil and crude oil;

[0031] Figure 9 a. Surface temperature change curve of PPy / PDMS sponge irradiated by xenon lamp;

[0032] Figure 10 a. Flow chart of the preparation method. DETAILED DESCRIPTION

[0033] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are part of, but not all of the embodiments of the present application; based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and the materials cited and referenced herein are incorporated by reference in their entirety.

[0035] All equivalents of the described specific embodiments that would be apparent to those skilled in the art upon a consideration of this application are intended to be included.

[0036] In the following examples, the experimental methods are all conventional methods unless otherwise specified. In the following examples, the instruments and equipment are all conventional laboratory instruments and equipment unless otherwise specified. In the following examples, the experimental materials are all purchased from conventional biochemical reagent stores unless otherwise specified.

[0037] The following examples are only three of the gradient experiments of the mass ratio of PDMS to liquid marbles LM being 0.8-1.2, and example 1 is the optimal group in the experimental group.

[0038] Example 1: A preparation method of a photothermal anti-sticking oil-water separation sponge, PDMS and PPy are used to prepare PPy / PDMS sponge, and the preparation flow is as shown in Figure 10 The steps are as follows:

[0039] (1) OTS-PPy: 0.2 g of polypyrrole was weighed and dispersed in 15 ml of N, N-dimethylformamide (DMF), 5:1 octadecyltrichlorosilane was added, and after ultrasonic dispersion in a low-power ultrasonic machine for 20 min, it was left to stand for 2 h to age, and then it was transferred to a centrifuge tube in a fume hood, centrifuged at a speed of 8000 r / min for 3 min, washed with ethanol for 3 times after centrifugation, and finally the polypyrrole powder was dried at 50°C.

[0040] (2) Preparation of PPy liquid beads: A certain mass of sodium alginate was dissolved in ultrapure water to obtain a 2wt%, 3wt%, and 5wt% sodium alginate aqueous solution, then 1 ml of a syringe was used to draw the 2wt%, 3wt%, and 5wt% sodium alginate aqueous solution and evenly drop-coat it on the culture dish covered with OTS-PPy powder, then the culture dish was rolled to evenly wrap the OTS-PPy powder with the sodium alginate, and after the liquid droplets contacted the powder, the culture dish was rolled for another 5 times to ensure that the liquid beads were covered with the same degree of powder particles, and then a small spoon was used to divide the liquid beads.

[0041] (3) Preparation of PDMS precursor solution: PDMS and the curing agent matched with it in Dow Corning Sylgard 184 PDMS were prepared in a mass ratio of 10:1, and 5% isopropyl alcohol was added to increase its flowability, and then mixed for 10 min at a speed of 2000 r / min by a vortex oscillator, and then degassed by a vacuum pump (2 Pa) to obtain the precursor solution.

[0042] (4) Liquid bead template shaping of the precursor solution: a silica gel mold with a size of 2 cm*2 cm*2 cm was taken, a layer of copper sheet was added inside to facilitate demolding, the prepared PPy liquid beads were transferred using weighing paper, 2.5 g of liquid beads were added, 2 g of precursor solution was added, and the liquid beads were mixed evenly with the precursor solution.

[0043] (5) Preparation of PPy / PDMS sponge: the mold was placed in a constant temperature oven for curing, the oven temperature was controlled at 80°C, the curing time was 3 h, the mold was removed and washed with ultrasonic water, and after several times of water washing, it was dried at 50°C for 90 min to obtain the PPy / PDMS sponge.

[0044] Example 2: A method for preparing a photothermal anti-adhesion oil-water separation sponge, the specific method is as follows:

[0045] (1) The method for preparing OTS-PPy is the same as that described in Example 1.

[0046] (2) The method for preparing PPy liquid beads is the same as that described in Example 1.

[0047] (3) The preparation method of the PDMS precursor solution is the same as that described in Example 1.

[0048] (4) The liquid marble template is used to shape the precursor solution: a silica gel mold with a size of 2 cm*2 cm*2 cm is taken, a copper sheet is added inside to facilitate demolding, the prepared PPy liquid marble is transferred using weighing paper, 2.5 g of the liquid marble is added, 3 g of the precursor solution is added, and the liquid marble and the precursor solution are uniformly mixed.

[0049] (5) The preparation method of the PPy / PDMS sponge is the same as that described in Example 1.

[0050] Example 3: A preparation method of a photothermal anti-adhesion oil-water separation sponge, Ag / PDMS sponge is prepared from PDMS and Ag, the preparation process is as shown in Figure 10 , and the steps are as follows:

[0051] (1) Preparation of Ag nanoparticles: 0.1 mol / L AgNO3 solution, 10 mg / mL polyvinylpyrrolidone (PVP) solution, and 0.01-0.2 mol / L sodium citrate solution are prepared, 100 mL of AgNO3 solution, 100 mL of PVP solution, and 100 mL of sodium citrate solution are accurately taken with a pipette into a 1000 mL round-bottom flask, 300 mL of distilled water is added, a stirring rod is placed in it, and then the round-bottom flask is fixed on an iron stand with a straight condenser tube, and the condenser water is introduced from the top. The round-bottom flask is placed in a 100℃ water bath on a magnetic stirrer, and heated for 2 h. After the reaction is completed, the round-bottom flask is taken out, and after cooling, the silver nanoparticle solution obtained under different sodium citrate solution concentrations and reaction conditions is transferred to different centrifuge tubes, and after centrifugal separation, the silver nanoparticles are obtained by vacuum drying at 50℃ for 2 h.

[0052] (2) OTS-Ag: 1 g of silver nanoparticles is dispersed in 25 ml of N,N-dimethylformamide (DMF), 5:1 of octadecyltrichlorosilane is added, and after ultrasonic dispersion for 20 min in a low-power ultrasonic machine, it is aged for 2 h, then it is transferred to a centrifuge tube in a fume hood, centrifuged at 8000 r / min for 3 min, washed with ethanol for 3 times after centrifugation, and finally the silver nanoparticles are dried at 40℃.

[0053] (3) Preparation method of Ag liquid beads: a certain amount of sodium alginate was dissolved in ultrapure water to obtain a 2wt% sodium alginate aqueous solution, then 1ml of the sodium alginate aqueous solution was taken with a syringe and uniformly dropped on the Petri dish full of Ag powder, then the Petri dish was rolled to make the sodium alginate uniformly wrap the Ag powder, after the liquid droplet contacted the powder, it was rolled for another five times to ensure that the liquid beads were covered with powder particles to the same extent, then the liquid beads were divided using a small spoon.

[0054] (4) The preparation method of the PDMS precursor solution is the same as that described in Example 1.

[0055] (5) Liquid bead template shaping of the precursor solution: a silica gel mold with a size of 2cm*2cm*2cm was taken, a layer of copper sheet was added inside to facilitate demolding, the prepared Ag liquid beads were transferred using weighing paper, 3g of Ag liquid beads were added, 2.1g of the precursor solution was added, and the liquid beads were mixed with the precursor solution uniformly.

[0056] (6) Preparation of Ag / PDMS sponge: the mold was placed in a constant temperature oven for curing, the oven temperature was controlled at 80℃, the curing time was 3h, the mold was removed and washed with ultrasonic water, after several times of water washing and cleaning, it was dried at 50℃ for 90min to obtain the Ag / PDMS sponge.

[0057] Example 4: A preparation method of a photothermal anti-adhesion oil-water separation sponge, PDMS and Ag were used to prepare Ag / PDMS sponge, the preparation process is as shown in Figure 10 , and the steps are as follows:

[0058] (1) The preparation method of Ag nanoparticles is the same as that described in Example 3.

[0059] (2) Octadecyltrichlorosilane (OTS) modified Ag, namely OTS-Ag, the preparation method is the same as that described in Example 3.

[0060] (3) Preparation method of Ag liquid beads: a certain amount of sodium alginate was dissolved in ultrapure water to obtain a 2wt% sodium alginate aqueous solution, then 1ml of the sodium alginate aqueous solution was taken with a syringe and uniformly dropped on the Petri dish full of Ag powder, then the Petri dish was rolled to make the sodium alginate uniformly wrap the Ag powder, after the liquid droplet contacted the powder, it was rolled for another five times to ensure that the liquid beads were covered with powder particles to the same extent, then the liquid beads were divided using a small spoon.

[0061] (4) The preparation method of the PDMS precursor solution is the same as that described in Example 1.

[0062] (5) Liquid bead template for precursor liquid shaping: take a silica gel mold with a size of 2 cm*2 cm*2 cm, add a layer of copper sheet inside to facilitate demolding, transfer the prepared PPy liquid bead using weighing paper, add 3 g of Ag liquid bead, and add 3.6 g of precursor liquid. Mix the precursor liquid of the liquid bead evenly.

[0063] (6) Preparation of Ag / PDMS sponge: place the mold in a constant temperature oven for curing, control the oven temperature to be 80°C, and the curing time is 3 h. Remove the mold and wash with ultrasonic water. After several times of water washing and cleaning, dry at 50°C for 90 min to obtain the Ag / PDMS sponge.

[0064] The liquid bead is a solid-liquid hybrid material formed by wrapping solid nanomaterials on the surface of liquid droplets, which has a certain mechanical strength, and loads a large amount of gas inside. Through heating, the gas can break the liquid bead and release to the polymer precursor to complete the pore forming. It is found through experimental verification that it is feasible to balance the mechanical strength and mechanical elasticity of the sponge material by foaming and pore forming to embed the nanomaterials on the surface of the sponge skeleton.

[0065] The digital photos and particle size distribution of the PPy liquid beads with different particle sizes prepared are shown in Figure 1 a and Figure 1 b, and the digital photos and particle size distribution of the Ag liquid beads with different particle sizes prepared are shown in Figure 2 a and Figure 2 b.

[0066] Figure 3 The SEM diagram of the photothermal anti-adhesion sponge prepared in Example 1, the influence of liquid bead embedding on the pore structure of the PPy / PDMS sponge was investigated by mercury injection experiment, from Figure 3 it can be seen that the sponge prepared by the liquid bead with larger pore size also has larger pore size.

[0067] Figure 4 and Figure 5 are the rebound time diagrams of the sponges prepared under the PDMS:LM=0.8 and PDMS:LM=1.2 ratios. From the diagram, it can be seen that by applying a weight of 1.5 kg, the sponge with a ratio of PDMS:LM=0.8 can have greater elastic deformation, but its elastic recovery time is less than 1 s, indicating that the prepared PPy / PDMS sponge has good mechanical elasticity and mechanical durability, and can be used as an ideal oil absorption material.

[0068] Figure 6 are the micro-morphologies of the PPy / PDMS sponge. Compared with the PDMS sponge, the PPy / PDMS sponge prepared by the liquid bead has more and larger pore diameters.

[0069] The contact angle was measured, and the results are shown in Figure 7As shown, it is found that the hydrophobicity of the PPy / PDMS sponge gradually increases with the increase of the PDMS:LM ratio, and when PDMS:LM = 0.9, the contact angle of the sponge is 129.05°. Further testing the underwater lipophilicity of the PPy / PDMS sponge, it can be observed that the sponge can absorb oil within 6s, fully showing the single selectivity of the sponge to oil and water.

[0070] Figure 8 The PPy / PDMS sponge has good hydrophobicity and a three-dimensional porous internal skeleton, and exhibits excellent selective adsorption of oil stains in an oil-water mixture.

[0071] The light-heat conversion efficiency of the sponge is evaluated by simulating the surface temperature change curve of the PPy / PDMS sponge under 1KW / m 2 The incident light is directly irradiated on the upper surface of the sample. Figure 9 The surface temperature detection image recorded by the infrared thermal imager is shown, so that the change of the temperature of the sample surface can be clearly observed, and the surface temperature of the PPy / PDMS sponge rapidly rises from room temperature to 65℃ within 5min and reaches equilibrium.

[0072] The present application can firmly inlay the modification on the surface of PDMS by embedding nanomaterials in the sponge, thereby enhancing the durability. The synergistic effect of the photo-induced heating effect and the surface anti-adhesion chemical modification is utilized to prepare the PPy / PDMS sponge, which can be used for cleaning high-viscosity and flow-resistant heavy oil pollution.

[0073] Example 5: A method for preparing a photo-thermal anti-adhesion sponge by liquid marble pore-making and in-situ surface inlaying, wherein the nanoparticles are graphene, the liquid is ethylene glycol, the rolling is performed for 15 times, the mass ratio of the PDMS precursor to the liquid marble is 1.0, and the rest of the method is the same as the method described in Example 1.

[0074] Example 6: A method for preparing a photo-thermal anti-adhesion sponge by liquid marble pore-making and in-situ surface inlaying, wherein the nanoparticles are a mixture of silver and polypyrrole at an arbitrary ratio, the liquid is water, the rolling is performed for 20 times, the mass ratio of the PDMS precursor to the liquid marble is 1.2, and the rest of the method is the same as the method described in Example 1.

[0075] Example 7: A method for preparing a photo-thermal anti-adhesion sponge by liquid marble pore-making and in-situ surface inlaying, wherein the nanoparticles are a mixture of polypyrrole and graphene at an arbitrary ratio, the liquid is water, the rolling is performed for 15 times, the mass ratio of the PDMS precursor to the liquid marble is 1.0, and the rest of the method is the same as the method described in Example 1.

[0076] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application; although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions recorded in the above embodiments can still be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing photothermal anti-adhesion sponge by liquid marble pore-forming and in-situ surface embedding, characterized in that: Solid-liquid hybrid liquid marbles are formed by rolling solid hydrophobic nanoparticles with photothermal effect with liquid. PDMS and curing agent are mixed to obtain a precursor liquid. Isopropanol is added to change the viscosity of the precursor liquid. The liquid marbles are transferred to the precursor liquid. Then, the curing temperature is controlled to make the liquid marbles break to complete the pore formation. The released solid nanomaterials are embedded in the precursor. By utilizing the synergistic effect of photothermal effect and surface anti-adhesion chemical modification, a photothermal anti-adhesion sponge with tunable pore structure and reusable properties is obtained. Wherein: the liquid is an aqueous solution of sodium alginate with a concentration of 2 wt%, the nanoparticles are polypyrrole, and the mass-to-volume ratio of hydrophobic nanoparticles to liquid is 1:5 g / μL; The specific method is as follows: (1) Preparation of liquid marbles: The nanoparticles are hydrophobically treated, and then the hydrophobic nanoparticles are laid flat on the substrate. The liquid is dropped onto the substrate covered with hydrophobic nanoparticles. The hydrophobic particles are rolled to autonomously coat the liquid droplets to form liquid marbles. (2) Preparation of PDMS precursor solution: PDMS and curing agent are mixed at a mass ratio of 1:0.

1. Isopropanol with a volume concentration of 20-30% is added at a mass ratio of PDMS to isopropanol of 1:0.05-0.

3. The mixture is mixed in a vortex mixer for 2 min and then evacuated by a 2Pa vacuum pump for 5 min to obtain the precursor solution. (3) Preparation of photothermal anti-adhesion sponge: 1g of the PDMS precursor liquid prepared in step (2) is drop-coated into the mold, and the liquid marble prepared in step (1) is transferred to the precursor liquid. After standing for 3-5 minutes, the liquid marble settles down, and then it is cured at a constant temperature of 30-90℃ for 2-3 hours to obtain the photothermal anti-adhesion sponge.

2. The preparation method according to claim 1, characterized in that: The specific method for hydrophobicating the nanoparticles in step (1) is as follows: 1g of nanoparticles are mixed with 254 μL of octadecyltrichlorosilane and 15ml of n-hexane, sonicated for 20min, allowed to stand for 2h, centrifuged at 8000 r / min, and vacuum dried at 50℃ for 2h to obtain hydrophobic nanoparticles; the mass-volume ratio of hydrophobic nanoparticles to liquid is 1:1-8g / μL; the number of rolling cycles is 10-20 times.

3. The preparation method according to claim 2, characterized in that: The number of scrolls is 10, 15, or 20.

4. The preparation method according to claim 1, characterized in that: In step (2), the mass ratio of PDMS to isopropanol is 1:0.

05.

5. The preparation method according to claim 1, characterized in that: In step (3), the liquid marbles are transferred into the precursor solution according to the mass ratio of PDMS precursor solution to liquid marbles of 0.8-1.

2.

6. The preparation method according to claim 5, characterized in that: In step (3), the mass ratio of PDMS precursor liquid to liquid marbles is 0.

8.

7. A photothermal anti-adhesion sponge obtained by the preparation method according to any one of claims 1-5.

8. The application of the photothermal anti-adhesion sponge according to claim 7 in the adsorption and removal of high-viscosity, non-flowing heavy oil contaminants.

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