A nanobowl array microreactor with a permeable membrane and its preparation method

Abstract

This invention belongs to the technical field of micro-nanoscale microreactor fabrication, specifically relating to a nanobowl array microreactor with a permeable membrane and its fabrication method, comprising the following steps: S1. Substrate pretreatment; S2. Self-assembling a PS sphere suspension onto the substrate pretreated in step S1 to prepare a PS sphere array; S3. Plasma etching of the PS sphere array from step S2; S4. Depositing the desired material on the sample surface from step S3; S5. Cleaning the sample from step S4 with a solvent. The substrate microreactor prepared by this invention consists of a bowl-shaped structure with controllable size and material, and its surface is covered with a thin layer of polystyrene. It can perform small molecule exchange while remaining unaffected by the external environment, and can be used in electrochemistry, photoelectrochemistry, and photocatalysis, with the potential for future applications in flow cells.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of micro-nano microreactor preparation, and particularly relates to a nano-bowl array microreactor with a permeable membrane and a preparation method thereof. BACKGROUND

[0002] With the continuous development of society and the continuous progress of nanotechnology, the concept of micro-nano microreactor is proposed, and the related research of micro-nano microreactor is gradually becoming one of the focuses of scientific workers. The electrochemical microreactor flow system generally includes an electrochemical microreactor, a micro flow system and a micro mixer. Since the microreaction technology emerged in the mid-1990s, the micro flow reaction system has been widely used in liquid phase reaction, gas-liquid reaction, photochemistry, electrochemistry and gas phase reaction. Compared with the traditional reactor process, the microreactor technology has many advantages such as high mass and heat transfer efficiency, short reaction time, no amplification effect, safety and reliability, high integration, and green production process, so the research and development of microreaction system are of great significance to the development of future chemical industry.

[0003] The existing microreactor is usually composed of many nanoarrays, such as a preparation method of a sub-micron optical microreactor in patent CN109900642A and a preparation method of a hollow nano-bowl structure in patent CN113512708A. Both of them form nanoarrays on the substrate, which has a complex process and needs expensive equipment support. At the same time, both microreactors directly contact with the reaction solution, which may be damaged and contaminated. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides a nano-bowl array microreactor with a permeable membrane and a preparation method thereof. It is limited by the shape of the hemispherical substrate on the one hand and protected by the ultra-thin permeable membrane based on PS on the other hand, and can be used in the fields of electrochemistry, photoelectrochemistry and photocatalysis.

[0005] The primary purpose of the present application is to provide a preparation method of a nano-bowl array microreactor with a permeable membrane.

[0006] The present application achieves the above-mentioned purpose through the following technical solutions:

[0007] A preparation method of a nano-bowl array microreactor with a permeable membrane, comprising the following steps:

[0008] S1, substrate pretreatment;

[0009] S2, self-assembling PS ball suspension liquid on the substrate treated in step S1 to prepare a PS ball array;

[0010] S3, plasma etching the PS ball array of step S2;

[0011] S4, depositing a desired material on the sample surface of step S3;

[0012] S5, cleaning the sample of step S4 with a dissoluble solvent;

[0013] The selected gas for the plasma etching of step S3 is oxygen or a mixture containing oxygen.

[0014] The present application finds that, through plasma etching of PS balls, the structure of the etched surface of the PS microspheres is changed slightly. The surface of the PS microspheres is affected by the oxygen plasma, which causes the polymer chains of the PS to break and combine with oxygen to form oxygen-containing functional groups such as hydroxyl and carboxyl groups. Meanwhile, cross-linking occurs between the polymer chains, like a disordered bundle of threads. However, since the oxygen plasma can only etch the surface of the PS microspheres, the interior of the PS balls can be dissolved while the surface cannot, thereby leaving a film on the surface. Since the interior of the PS balls is not etched, it is dissolved and cleaned by the organic solvent to form a hollow bowl structure. Some molecules can pass through the film to react with the substrate, while unwanted impurities cannot penetrate and can thus provide protection.

[0015] Preferably, the substrate of step S1 is conductive glass, common glass sheet with deposited metal, or metal sheet, which is cleaned by ultrasonic cleaning with acetone, anhydrous ethanol, and deionized water for 5-20 min.

[0016] Preferably, the PS balls of step S2 have a diameter of ≥500 nm, and the PS ball array is prepared by surface tension self-assembly, air-liquid surface self-assembly, or spin coating.

[0017] Preferably, the plasma etching of step S3 is performed at a power of 10-200 w for 1-600 s, and the selected gas is flowed at a rate of 1-100 sccm.

[0018] Preferably, the material of step S4 is one or more of a metal and a semiconductor.

[0019] Preferably, the material deposition method of step S4 includes electrodeposition and sol-gel method.

[0020] Preferably, the dissoluble solvent of step S5 is an organic solvent or solvent mixture that can dissolve PS, including tetrahydrofuran, toluene, acetone, and cyclohexane.

[0021] The present application also provides a nano-bowl array microreactor with a permeable film, which is prepared by the above method.

[0022] The present application provides a substrate microreactor, the surface of which is combined with polystyrene to form a microreaction system as a whole. Firstly, the interior of the reactor is a bowl-shaped structure, and the surface of the bowl is an ultrathin PS film, so that the reactor is not affected by the external environment during the reaction, and the PS film has permeability, which can ensure the exchange of small molecules and promote the phase separation interface between two immiscible solvents. Secondly, the shape of the reactor is a bowl-shaped array structure, and each bowl can be regarded as a micro condenser, which can collect more light, at the same time, the periodic nanometer array has a surface plasmon effect, which can further enhance light absorption.

[0023] At the same time, the microreactor of the present application has a controllable size and shape, and different metals and semiconductors can be deposited according to the needs. Electrochemical and photoelectrochemical reactions can be carried out by applying electrode potential, and it has good application in the fields of electrochemistry, photoelectrochemistry and photocatalysis, and is expected to be used in future flow battery applications.

[0024] The present application also protects the application of the above-mentioned nanobowl array microreactor with permeable film in electrochemical, photoelectrochemical and photocatalytic reactions.

[0025] Compared with the prior art, the present application has the following beneficial effects:

[0026] (1) Compared with the existing microreactor, the interior of the microreactor in the present application is a bowl-shaped array structure, and the top of the bowl is covered with an ultrathin PS film, so that the reactor is not affected by the external environment during the reaction, and the PS film has permeability, which can promote the phase separation interface between two immiscible solvents and ensure the mutual exchange of small molecules in the solution.

[0027] (2) Compared with the existing microreactor, the microreactor in the present application has a nanobowl-shaped array structure, has a controllable nanobowl size and shape, and can deposit the required metal or semiconductor. Each bowl can act as a micro condenser, has a condensing effect, and at the same time, the nanobowl array has a plasmon effect and a larger specific surface area, which can further enhance light absorption and greatly improve the performance of the reactor.

[0028] (3) Compared with the existing microreactor, the microreactor in the present application is a substrate microreactor, which can carry out electrochemical and photoelectrochemical reactions by applying electrode potential, and at the same time, can increase the light condensation of photochemical reaction and the integration of flow cell. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is a process flow diagram of the present application.

[0030] Figure 2are the structural schematic diagrams of each process of the present application, (a) is a prepared substrate, (b) is a self-assembled PS ball array on the substrate, (c) is a PS ball array etched by radio frequency plasma, (d) is a desired material deposited on the sample surface, and (e) is a nano-bowl structure micro-reactor obtained after the internal PS balls are removed by a dissolvable solution.

[0031] Figure 3 are SEM surface and cross-section diagrams of different steps of Comparative Example 1, A is the surface and cross-section of a 500 nm PS ball array self-assembled on a copper-plated glass sheet, B is the surface and cross-section after a proper amount of copper is electrodeposited, and C is the surface and cross-section of a nano-bowl array obtained after the internal PS balls are dissolved by THF.

[0032] Figure 4 are SEM surface and cross-section diagrams of different steps of Example 1, A is the surface and cross-section of a 500 nm PS ball array self-assembled on a copper-plated glass sheet, B is the surface and cross-section after the PS ball array is etched by radio frequency plasma, C is the surface and cross-section after a proper amount of copper is electrodeposited, and D is the surface and cross-section of a nano-bowl array micro-reactor with a permeable film obtained after the internal PS balls are dissolved by THF. DETAILED DESCRIPTION

[0033] The technical solutions of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0034] The test methods used in the embodiments of the present application are all conventional methods unless otherwise specified; and the materials, reagents, etc. used are all commercially available reagents and materials unless otherwise specified.

[0035] Example 1

[0036] A preparation method of a nano-bowl array micro-reactor with a permeable film comprises the following steps:

[0037] S1, cleaning of a glass sheet: first cut the glass sheet into a size of 2 cm*3 cm, sequentially clean with acetone, isopropyl alcohol, anhydrous ethanol, and deionized water for 10 minutes, and finally dry under a nitrogen stream.

[0038] S2, vacuum electron beam evaporation of titanium and copper film: first turn on the instrument, open the cavity under correct operation, stick the glass sheet on the sample disc of the EBE with high-temperature resistant double-sided tape, then close the cavity and evacuate, when the vacuum degree is lower than 7.5*10 -4Pa, after selecting titanium and copper and thickness in the program settings, click start, slowly adjust the beam current of the electron gun to about 40 to pre-melt, wait until the titanium in the crucible is fully melted, open the baffle, then slowly increase the beam current to about 70, keep the evaporation rate at about 0.5, when the thickness of titanium reaches 100 nm, close the baffle, adjust the beam current knob to the minimum. Automatically switch to the copper crucible, slowly increase the beam current to about 30 to pre-melt, when the copper in the crucible is fully melted, open the baffle, then slowly increase the beam current to about 40, keep the evaporation rate at about 0.5, when the thickness of copper reaches 100 nm, close the baffle, adjust the beam current knob to the minimum, turn off the electron gun, open the automatic stop, when the molecular pump speed is zero, open the air valve, open the chamber door and take out the sample, at this time the copper-coated glass substrate is obtained.

[0039] S3, PS ball array preparation: a 30 cm diameter culture dish is washed with ultrapure water and filled with ultrapure water, and then placed for 10 min. A 500 nm PS ball solution is prepared (PS: 1% H2SO4: 1% styrene = 300: 300: 10). After preparation, ultrasonic oscillation is performed for 10 min. Then a special elbow bus dropper is used to take the solution to 1 / 3 of the dropper. The dropper tip is removed, and the dropper is kept at an angle of about 45°. One end of the dropper is slowly placed in the middle of the culture dish until the elbow just touches the liquid surface. At this time, the PS ball solution slowly flows out and spreads to form a circle. When the PS film covers the edge of the culture dish and leaves a 1 / 5 small circle in the middle, stop. After the dropper is removed, the PS ball film will gather in the middle and fill the entire culture dish. After self-assembly for one hour, slowly add SDS along the edge to make the film gather in the middle of the culture dish. After completion, use tweezers to hold one corner of the substrate and slowly place it in water around the blank area. Then slowly pull it up at an angle of 45° in the film area. After natural air drying, a neat PS ball array on the substrate is obtained.

[0040] S4, plasma etching of PS ball array: turn on the power switch of the plasma cleaner, open the cavity and place the sample and vacuumize. When the vacuum degree is less than 20 Pa, open gas valve one. At this time, gas valve one is connected to the indoor air, and the gas flow rate is set to 10 sccm. At this time, the cavity pressure will first increase and then slowly decrease. When the pressure is less than 38 Pa, set the etching power to 30 W and the etching time to 150 s. Turn on the radio frequency switch. At this time, there will be a glow in the cavity, indicating that etching is in progress. After completion, open the cavity and take out the sample.

[0041] S5. Electrodeposition of Copper: The electrolyte is prepared by dissolving 2.25g CuSO4·5H2O in 1L of ultrapure water, resulting in a concentration of 9mM / L. Concentrated sulfuric acid is then slowly added dropwise to adjust the pH to approximately 1.35. Electrodeposition is performed using a three-electrode system in a 100mL electrolytic cell chamber. A potentiostat (Chininstrument 600E) is used to control the potential. The counter electrode is a platinum sheet electrode, and the reference electrode is Ag / AgCl (3M KCl). First, one end of the sample is clamped with the working electrode clamp, and a multimeter is used to confirm a proper connection between the sample and the clamp. Approximately 60ml of electrolyte is slowly added to the electrolytic cell, bringing the solution to about half its height. The three electrodes are then inserted into the holes in the electrolytic cell lid, and the lid is closed. All three electrodes are now submerged in the liquid. The height of the working electrode clamp is adjusted so that the sample is submerged while the clamp is above the liquid surface. Connect the working electrode, reference electrode, and counter electrode using the electrode wires of the electrochemical workstation. Turn on the electrochemical workstation and related software, select the relevant current-time mode, set the voltage to -0.427V, and the time to 600s. After electrodeposition begins, small bubbles can be observed on the sample surface. After the time is up, remove the sample and rinse it with anhydrous ethanol, then dry it under a nitrogen flow.

[0042] S6. Dissolving internal PS microspheres with THF: Place the sample in a beaker containing THF, let it stand for one hour, then remove it, rinse with anhydrous ethanol, and dry under a nitrogen stream.

[0043] Example 2

[0044] A method for preparing a nanobowl array microreactor with a permeable membrane includes the following steps:

[0045] S1. Cleaning of glass slides: First, cut the glass slides into 2cm*3cm pieces, and then clean them with acetone, isopropanol, anhydrous ethanol, and deionized water in sequence for 10 minutes using ultrasonic cleaning. Finally, dry them under a nitrogen flow.

[0046] S2. Vacuum Electron Beam Evaporation of Titanium and Copper Films: First, turn on the instrument and open the chamber under correct operation. Neatly attach the glass slides to the EBE sample tray using high-temperature resistant double-sided tape. Then close the chamber and evacuate the vacuum. When the vacuum level is below 7.5 × 10⁻⁶... -4At Pa, select titanium, copper, and thickness in the program settings and click start. Slowly adjust the electron gun beam current to around 40 for pre-melting. After the titanium in the crucible has fully melted, open the baffle and slowly increase the beam current to around 70, maintaining a deposition rate of around 0.5. When the titanium thickness reaches 100 nm, close the baffle and adjust the beam current knob to the minimum. Automatically switch to the copper crucible and slowly increase the beam current to around 30 for pre-melting. After the copper in the crucible has fully melted, open the baffle and slowly increase the beam current to around 40, maintaining a deposition rate of around 0.5. When the copper thickness reaches 100 nm, close the baffle, adjust the beam current knob to the minimum, turn off the electron gun, and activate automatic shutdown. When the molecular pump speed reaches zero, open the air valve, open the chamber door, and remove the sample. At this point, a copper-plated glass substrate is obtained.

[0047] S3. PS Sphere Array Preparation: Clean and fill a 30cm diameter culture dish with ultrapure water, let it stand for 10 minutes, prepare a 2000nm PS sphere solution (PS:ethanol = 430:300), and sonicate for 10 minutes. Then, use a specially designed bent-tip Buster dropper to draw the solution to 3 / 4 of the dropper's length, remove the dropper tip, and keep the dropper tilted at approximately 45°. Slowly place one end of the dropper into the center of the culture dish until the bend just touches the liquid surface. At this point, the PS sphere solution will slowly flow out and spread outward to form a circle. Stop when the PS membrane covers the edge of the culture dish, leaving a small blank circle in the center. After removing the dropper, the PS sphere membrane will gather towards the center and fill the entire culture dish. After one hour of self-assembly, slowly add SDS along the edge to allow the membrane to gather in the center of the culture dish. After completion, hold one corner of the substrate with tweezers and slowly immerse it in water in the surrounding blank area. Then, slowly lift the membrane area at a 45° angle upwards. After air drying, a neatly arranged PS sphere array on the substrate is obtained.

[0048] S4. Plasma Etching of PS Ball Array: Turn on the power switch of the plasma cleaner, open the chamber, place the sample in, and evacuate. When the vacuum level is lower than 20Pa, open gas valve one. At this time, gas valve one is connected to the indoor air. Set the gas flow rate to 10sccm. At this time, the chamber pressure will first increase and then slowly decrease. When the pressure is less than 38Pa, set the etching power to 30W and the etching time to 300s. Turn on the RF switch. At this time, there will be glow in the chamber, indicating that etching is in progress. After completion, open the chamber and take out the sample.

[0049] S5. Electrodeposition of Nickel: The electrolyte is prepared as 0.2M nickel sulfate + 0.1M nickel chloride, with the pH adjusted to 6 using ammonia. Electrodeposition is performed using a three-electrode system in a 200 mL electrolytic cell chamber. A potentiostat (Chininstrument 600 E) is used to control the current. The counter electrode is a platinum sheet electrode, and the reference electrode is Ag / AgCl (3M KCl). First, clamp one end of the sample with the working electrode clamp and use a multimeter to confirm that the sample and electrode clamp are properly connected. Slowly add about 120 mL of electrolyte to the electrolytic cell. To facilitate better reduction of nickel ions, a magnetic rotor is added to the electrolytic cell and set to a rotation speed of 300 rpm. Insert the three electrodes into the holes in the electrolytic cell lid and close the lid. At this point, all three electrodes are below the liquid surface. Adjust the height of the working electrode clamp so that the sample is below the liquid surface while the electrode clamp is above the liquid surface. Connect the working electrode, reference electrode, and counter electrode using the electrode wires of the electrochemical workstation. Turn on the electrochemical workstation and related software, select the relevant multi-terminal current mode, set the current to -0.001A, and the time to 600s. After electrodeposition begins, small bubbles can be observed on the sample surface. After the time is up, remove the sample and rinse it with ultrapure water, then dry it under a nitrogen flow.

[0050] S6. Dissolving internal PS microspheres with THF: Place the sample in a beaker containing THF, let it stand for one hour, then remove it, rinse with anhydrous ethanol, and dry under a nitrogen stream.

[0051] Example 3

[0052] A method for preparing a nanobowl array microreactor with a permeable membrane includes the following steps:

[0053] S1. Hydrophilic treatment of glass slides: First, cut the glass slides into 2cm*3cm pieces, soak them in piranha solution for 5 minutes, rinse them with plenty of deionized water, and finally dry them under a nitrogen flow.

[0054] S2. PS sphere array preparation: Clean a 30cm diameter culture dish with ultrapure water and fill it completely. Let it stand for 10 minutes. Prepare an 800nm ​​PS sphere solution (PS: 1% H2SO4: 1% styrene = 300: 300: 10). After preparation, sonicate for 10 minutes. Then, use a specially designed bent-end Buster dropper to draw the solution to 1 / 3 of the dropper's length. Remove the dropper tip and keep the dropper tilted at about 45°. Slowly place one end of the dropper into the center of the culture dish until the bend just touches the liquid surface. At this point, the PS sphere solution will slowly flow out and spread outward to form a circle. Stop when the PS membrane covers the edge of the culture dish and there is only a 1 / 5 blank circle in the center. After removing the dropper, the PS sphere membrane will gather towards the center and fill the entire culture dish. After one hour of self-assembly, slowly add SDS along the edge to make the membrane gather in the center of the culture dish. After completion, hold one corner of the substrate with tweezers and slowly place it into the water in the surrounding blank area. Then, slowly lift it upwards at a 45° angle in the film area. After air drying, you will get a neat array of PS spheres on the substrate.

[0055] S3. Plasma Etching of PS Ball Array: Turn on the power switch of the plasma cleaner, open the chamber, place the sample in, and evacuate. When the vacuum level is lower than 20Pa, open gas valve one. At this time, gas valve one is connected to the indoor air. Set the gas flow rate to 10sccm. At this time, the chamber pressure will first increase and then slowly decrease. When the pressure is less than 38Pa, set the etching power to 30W and the etching time to 150s. Turn on the RF switch. At this time, there will be glow in the chamber, indicating that etching is in progress. After completion, open the chamber and take out the sample.

[0056] S4. Deposition of titanium dioxide using the sol-gel method: The titanium dioxide sol is prepared as follows: ① Add 5 mL of tetrabutyl titanate to 25 mL of anhydrous ethanol and stir for 10 min. Then add the required amount of 0.3 g PVP and stir for 30 min until completely dissolved to obtain solution A. ② Dissolve 4 mL of deionized water in 75 mL of anhydrous ethanol and stir for 10 min. Then add glacial acetic acid to adjust the pH to between 3.0 and 3.4, mix and stir for 10 min to obtain solution B. ③ Add solution B to solution A at a rate of 90 drops / min, stir for 40 min, and age for 24 h to obtain the desired sol. Use a pipette to slowly drop 60 μL of the titanium dioxide sol onto the sample, and then allow it to air dry.

[0057] S5. Dissolving internal PS microspheres with THF: Place the sample in a beaker containing THF, let it stand for one hour, then remove it, rinse with anhydrous ethanol, and dry under a nitrogen stream.

[0058] Comparative Example 1

[0059] The difference between Comparative Example 1 and Example 1 is that step S3 is omitted and the sample is not plasma etched. The other preparation methods are the same as in Example 1, and will not be repeated here.

[0060] Comparative Example 2

[0061] The difference between Comparative Example 2 and Example 1 is that argon is used when plasma etching the sample in step S3. The other preparation methods are the same as in Example 1 and will not be repeated here.

[0062] Morphological structure characterization and analysis

[0063] The morphology of the nanobowl array microreactor prepared in Example 1 was characterized, and the results are shown in the figure. Figure 3 .

[0064] like Figure 3 As shown, in Comparative Example 1, since there is no plasma etching process, the PS microspheres are easily dissolved by organic solvents such as tetrahydrofuran, thus directly obtaining a nanobowl array.

[0065] In Comparative Example 2, the etching process used argon gas. Under the bombardment of argon plasma, the PS microspheres were directly removed, so the polystyrene film no longer existed on the surface, and a nanobowl array was directly obtained.

[0066] The morphology of the nanobowl array microreactor prepared in Example 1 was characterized, and the results are shown in the figure. Figure 4 .

[0067] like Figure 4 As shown, Figure A is an SEM image of the surface and cross-section of the self-assembled PS microsphere array on the substrate. Figure B is an SEM image of the sample surface and cross-section after 150 s of etching with oxygen plasma. It can be clearly seen that the gap between the spheres has increased. This is because the reaction between the oxygen plasma and the surface of the PS microspheres causes the PS microspheres to shrink. At the same time, the addition of oxygen plasma causes the polystyrene polymer chains to break, recombine and entangle with each other. Figure C is an SEM image of the surface and cross-section of the sample after copper electrodeposition for a certain period of time. It can be seen that the copper slowly grows from the bottom to the hemisphere of the PS microsphere. Figure D is an SEM image of the surface and cross-section of the sample after cleaning with tetrahydrofuran for 24 h. Due to the action of oxygen plasma on the surface of the PS microspheres, the polystyrene polymer chains break and combine with oxygen to form oxygen-containing functional groups such as hydroxyl and carboxyl groups. At the same time, cross-linking occurs between the polymer chains, like a tangled ball of yarn. However, since the oxygen plasma can only etch the surface part of the PS microspheres, the inside of the PS spheres can be dissolved but the surface cannot, ultimately forming a nanobowl-shaped cavity covered by a PS film.

[0068] Obviously, the specific implementation schemes described above are merely a further detailed explanation of the purpose, technical solution and beneficial effects of the present invention. It should be understood that the above descriptions are only specific examples of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A nanobowl array microreactor with permeable membrane, characterized in that, The preparation comprises the following steps: S1, substrate pretreatment; S2, self-assembly of PS ball suspension on the substrate treated in step S1 to prepare PS ball array; S3, plasma etching of the PS ball array in step S2; S4, deposition of desired material on the surface of the sample in step S3; S5, cleaning of the sample in step S4 with a dissoluble solvent; The selected gas for plasma etching in step S3 is oxygen; The material deposition method in step S4 is electrodeposition or sol method; The interior of the nanobowl array microreactor is a bowl structure, the surface of the bowl is an ultrathin PS film, and the surface deposited material is one or more of metal and semiconductor.

2. The nanobowl array microreactor with permeable membrane according to claim 1, wherein, The substrate in step S1 is conductive glass, common glass sheet with deposited metal or metal sheet, and the pretreatment process is ultrasonic cleaning with acetone, anhydrous ethanol and deionized water for 5-20 min.

3. The nanobowl array microreactor with permeable membrane according to claim 1, wherein, The diameter of the PS ball in step S2 is ≥500 nm, and the PS ball array is prepared by surface tension self-assembly, air-liquid surface self-assembly or spin coating method.

4. The nanobowl array microreactor with permeable membrane according to claim 1, wherein, The selected power for plasma etching in step S3 is 10-200 w, the etching time is 1-600 s, and the selected gas flow rate is 1-100 sccm.

5. The nanobowl array microreactor with permeable membrane according to claim 1, wherein, The dissoluble solvent in step S5 is an organic solvent or solvent mixture that can dissolve polystyrene, including tetrahydrofuran, toluene, acetone and cyclohexane.

6. Application of the nanobowl array microreactor with permeable film in electrochemistry, photoelectrochemistry or photocatalysis reaction according to claim 1.

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