Standing type critical plane electrochemical hydrogen peroxide generation device and hydrogen peroxide preparation method and application thereof

Abstract

The invention relates to the technical field of hydrogen peroxide electrochemical preparation, in particular to a standing type critical plane electrochemical hydrogen peroxide generation device and a hydrogen peroxide preparation method and application thereof.The standing type critical plane electrochemical hydrogen peroxide generation device comprises a box body, the box body is provided with a containing cavity, and one side of the box body is provided with a box body opening, a cathode assembly close to the box body opening and an anode assembly away from the box body opening; the cathode assembly is provided with a hydrophobic breathable layer, the hydrophobic breathable layer is provided with an adjacent-phase interface reaction area communicated with the opening of the box body, one side of the adjacent-phase interface reaction area and air of the opening of the box body form a gas-solid critical plane, and the other side of the adjacent-phase interface reaction area and the electrolyte of the containing cavity form a solid-liquid critical plane. According to the invention, the adjacent phase interface reaction area is arranged, so that one side of the cathode assembly and air at the opening of the box body form a gas-solid critical plane, oxygen can be fully utilized by the cathode, and the other side of the adjacent phase interface reaction area and electrolyte in the accommodating cavity form a solid-liquid critical plane, so that the reaction can be continuously carried out; and continuous preparation of high-concentration products is ensured.

Description

Technical Field

[0001] The invention relates to the technical field of electrochemical preparation of hydrogen peroxide, in particular to a stationary critical surface electrochemical hydrogen peroxide generating device, and a hydrogen peroxide preparation method and application thereof. Background Art

[0002] An electrochemical device is a device that can convert electrical energy into chemical energy. It consists of a power source, a cathode and an anode, and an electrolyte solution or a molten electrolyte. When an external power source is connected, current passes through the electrolyte, and reduction and oxidation reactions occur at the cathode and anode, respectively.

[0003] Hydrogen peroxide is a strong oxidizing liquid with the advantages of high efficiency, environmental protection, and no pollution residue. It is known as a "green oxidant" and is widely used in bleaching, disinfection, water treatment, chemical synthesis and other fields. At present, there are many methods for preparing hydrogen peroxide, but they all have certain limitations. Although traditional chemical synthesis methods such as the anthraquinone method can be produced on a large scale, the process is complex, energy consumption is high, and may cause environmental pollution problems. In the traditional electrochemical preparation process of hydrogen peroxide, it has attracted much attention due to its simple equipment, convenient operation, and high product purity.

[0004] In the process of electrolytic preparation of hydrogen peroxide, its cathode needs to consume dissolved oxygen to promote the reaction. However, due to the limitation of dissolved oxygen in water, the efficiency and equilibrium concentration of electrochemical synthesis products cannot be improved during the reaction, affecting the continuous preparation of high-concentration products. In practical applications, users have an increasing demand for real-time preparation of high-concentration hydrogen peroxide. However, existing electrochemical preparation technologies are difficult to achieve high-concentration production while ensuring efficiency. In view of the challenges faced by electrochemical preparation methods in improving the concentration and stability of hydrogen peroxide, it is necessary to improve the structure of the electrochemical device to improve the efficiency and equilibrium concentration of electrochemical synthesis products and further improve the reaction performance and stability. Summary of the invention

[0005] In view of the technical problem that in the electrolysis process mentioned above, the cathode needs to consume dissolved oxygen to promote the reaction, and the efficiency and equilibrium concentration of the electrochemical synthesis product cannot be improved during the reaction process due to the limitation of the dissolved oxygen content in the water, which affects the continuous preparation of high-concentration products, the technical solution adopted by the present invention to solve the technical problem is: A static critical surface electrochemical hydrogen peroxide generating device comprises a box body, wherein the box body is provided with a containing cavity, one side of the box body is provided with a box body opening connected with the containing cavity, a cathode assembly located in the containing cavity and close to the box body opening, and an anode assembly located in the containing cavity and away from the box body opening, wherein the cathode assembly is provided with a hydrophobic air-permeable layer, and the hydrophobic air-permeable layer is provided with a phase interface reaction zone connected with the box body opening, one side of the phase interface reaction zone forms a gas-solid critical surface with the air of the box body opening, and the other side forms a solid-liquid critical surface with the electrolyte in the containing cavity.

[0006] Furthermore, the cathode assembly includes a cathode support close to the box opening and a cathode plate connected to the cathode support, the anode assembly includes an anode support away from the box opening and an anode plate connected to the anode support, the cathode support is provided with a cathode support opening connected to the box opening, the cathode plate is connected to the box opening through the cathode support opening, the anode support is provided with an anode support opening connected to the accommodating cavity, and the hydrophobic air-permeable layer is located on the cathode plate.

[0007] Furthermore, the distance between the anode sheet and the cathode sheet is between 2-50 mm, the anode sheet adopts a metal coating substrate, the cathode sheet adopts a conductive inert metal material, the cathode sheet is provided with a cathode catalyst layer, and the hydrophobic breathable layer includes a cathode catalyst layer and a hydrophobic breathable resin.

[0008] Furthermore, the anode plate is made of one of platinum-plated, iridium-tantalum or tin-antimony coated titanium substrates, with a coating thickness of 0.1μm-1μm, and the cathode plate is made of one of aluminum, titanium, stainless steel, nickel, and platinum-titanium.

[0009] Furthermore, the cathode catalyst layer adopts a nano-carbon-based catalyst, and the hydrophobic and breathable layer is made by mixing the cathode catalyst layer and a hydrophobic and breathable resin.

[0010] Furthermore, the box body is provided with a first limit frame for fixing the cathode support, and a second limit frame for fixing the anode support, the cathode support and the anode support are arranged opposite to each other, the cathode sheet and the anode sheet are arranged opposite to each other, and the second limit frame is provided with a plurality of limit grooves for the anode support to extend into, and the plurality of limit grooves are arranged at intervals.

[0011] Further, the cathode support includes a first cathode support, a second cathode support, and a cathode support accommodating cavity located between the first cathode support and the second cathode support, and the cathode sheet is located in the cathode support accommodating cavity; the anode support includes a first anode support, a second anode support, and an anode support accommodating cavity located between the first anode support and the second anode support, and the anode sheet is located in the anode support accommodating cavity; the cathode support openings are respectively arranged on the first cathode support and the second cathode support, and the anode support openings are respectively arranged on the first anode support and the second anode support.

[0012] Further, the first cathode support is provided with a cathode support clamping portion, the second cathode support is provided with a cathode support connecting portion which cooperates with the cathode support clamping portion, the first anode support is provided with an anode support clamping portion, the second anode support is provided with an anode support connecting portion which cooperates with the anode support clamping portion, the cathode support is provided with a cathode support connecting groove for extending one end of the cathode sheet to be connected to an external power supply, and the anode support is provided with an anode support connecting groove for extending one end of the anode sheet to be connected to an external power supply.

[0013] Furthermore, the present invention also provides a method for preparing hydrogen peroxide using a stationary critical surface electrochemical hydrogen peroxide generator, comprising the stationary critical surface electrochemical hydrogen peroxide generator as described above, and the preparation method comprises the following steps: S1, the cathode assembly and the anode assembly are respectively fixed in the accommodating cavity, and one side of the cathode assembly is connected to the box opening; S2, the cathode assembly and the anode assembly are electrically connected to an external power supply through wires, and an electrolyte is added to the water tank. One side of the phase interface reaction zone forms a gas-solid critical surface with the air at the box opening, and the electrolyte on the other side of the phase interface reaction zone forms a solid-liquid critical surface; S3. After power is input, the cathode assembly forms a gas-solid-liquid critical surface, the oxygen generated by the anode assembly reaches the solid-liquid critical surface of the adjacent phase interface reaction zone, and the oxygen in the air enters the cathode assembly through the gas-solid critical surface of the adjacent phase interface reaction zone for replenishment, thereby producing hydrogen peroxide.

[0014] Furthermore, the present invention also provides the application of a stationary critical surface electrochemical hydrogen peroxide generating device, and the prepared hydrogen peroxide is applied to water purification, environmental disinfection, and food processing.

[0015] The beneficial effects of the present invention are as follows: 1. The present invention forms a gas-solid critical surface with one side of the cathode assembly and the air in the box opening by setting a phase interface reaction zone, thereby increasing the contact area between the cathode and oxygen in the air, so that oxygen can be more fully utilized by the cathode assembly, providing a continuous oxygen supply for the cathode assembly reaction, and the other side of the phase interface reaction zone forms a solid-liquid critical surface with the electrolyte in the accommodating chamber, so that the reaction can proceed continuously, thereby improving the efficiency and equilibrium concentration of the electrochemical synthesis product and ensuring the continuous preparation of high-concentration products.

[0016] 2. The present invention can prepare high-concentration hydrogen peroxide, which can be widely used in many fields such as water purification, environmental disinfection, food processing, etc. Compared with the traditional preparation process, the present invention has significant improvements in equipment integration, energy conversion efficiency, product application scenarios, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic diagram of the static critical surface electrochemical hydrogen peroxide generating device of the present invention.

[0018] Figure 2 This is a schematic diagram from another perspective of the static critical surface electrochemical hydrogen peroxide generating device of the present invention.

[0019] Figure 3 for Figure 2 AA section view.

[0020] Figure 4 for Figure 3 Enlarged view of part B.

[0021] Figure 5 It is an exploded view of the static critical surface electrochemical hydrogen peroxide generating device of the present invention.

[0022] Figure 6 FIG. 4 is a schematic diagram of a static critical surface electrochemical hydrogen peroxide generating device in another embodiment of the present invention.

[0023] Figure 7 for Figure 6 CC cross-sectional view.

[0024] Figure 8 for Figure 7 Enlarged view of part D.

[0025] Fig. 9 FIG. 1 is an exploded view of a stationary critical surface electrochemical hydrogen peroxide generating device in another embodiment of the present invention.

[0026] Fig.10 FIG. 1 is an exploded view of a stationary critical surface electrochemical hydrogen peroxide generating device in another embodiment of the present invention.

[0027] Fig.11The data are test data of the static critical surface electrochemical hydrogen peroxide generating device of the present invention.

[0028] Fig.12 The test data of the static critical surface electrochemical hydrogen peroxide generating device in another embodiment of the present invention. DETAILED DESCRIPTION

[0029] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0030] like Figures 1 to 10 The static critical surface electrochemical hydrogen peroxide generating device shown comprises a box body 1, wherein the box body 1 is provided with a containing cavity 11, one side of the box body 1 is provided with a box body opening 12 connected with the containing cavity 11, a cathode assembly 3 located in the containing cavity 11 and close to the box body opening 12, and an anode assembly 4 located in the containing cavity 11 and away from the box body opening 12, wherein the cathode assembly 3 is provided with a hydrophobic air-permeable layer, and the hydrophobic air-permeable layer is provided with a phase interface reaction zone 30 connected with the box body opening 12, one side of the phase interface reaction zone 30 forms a gas-solid critical surface with the air of the box body opening 12, and the other side forms a solid-liquid critical surface with the electrolyte in the containing cavity 11.

[0031] Compared with the traditional device, the present invention no longer relies solely on the limited dissolved oxygen in the water to supply the cathode reaction. The present invention sets a phase interface reaction zone so that one side of the cathode assembly forms a gas-solid critical surface with the air at the box opening, thereby increasing the contact area between the cathode and the oxygen in the air, so that the oxygen can be more fully utilized by the cathode, providing a continuous oxygen supply for the cathode reaction. The other side of the phase interface reaction zone forms a solid-liquid critical surface with the electrolyte in the accommodating chamber, so that the reaction can continue, thereby improving the efficiency and equilibrium concentration of the electrochemical synthesis product and ensuring the continuous preparation of high-concentration products.

[0032] Furthermore, when the other side of the cathode assembly forms a solid-liquid critical surface with the electrolyte in the accommodating cavity, such a setting enables the electrolyte to fully contact the cathode assembly, providing the necessary environment for the electrochemical reaction. The surrounding electrolyte environment is stable and suitable for the reaction, which is conducive to the rapid transfer of oxygen from the gas-solid critical surface to the solid-liquid critical surface, and then participates in the cathode reaction, thereby improving the efficiency of oxygen participating in the reaction. At the same time, the existence of the solid-liquid critical surface also contributes to the uniform distribution and flow of the electrolyte, further promoting the reaction. At this time, the cathode assembly forms a gas-solid-liquid critical surface.

[0033] During the electrolytic preparation of hydrogen peroxide, under the critical surface state, oxygen can diffuse through the critical surface to the cathode surface. During the electrochemical reaction, oxygen reduction reaction occurs on the cathode surface to generate hydrogen peroxide: O 2 + 2H + +2e- → H 2 O 2 ; At the same time, water or oxygen oxidation reaction occurs on the anode surface to generate oxygen: 2H 2 O → O 2 + 4H + +4e - ; The overall reaction formula of the entire electrolysis process is 2H 2 O + O 2 →2H 2 O 2 .

[0034] The present invention provides a phase interface reaction zone, which is beneficial for rapid transfer of oxygen from the gas-solid critical surface to the solid-liquid critical surface, and then participates in the cathode reaction, thereby promoting the reaction and improving the continuous preparation efficiency of high-concentration hydrogen peroxide.

[0035] Optionally, in some embodiments, the contact depth between the cathode electrode and the electrolyte surface, as well as the height difference between the box opening and the electrolyte surface can be controlled so that the interface reaction zone can be connected to the box opening while the electrolyte surface will not flow out from the lowest position of the box opening, thereby achieving the formation of a gas-liquid-solid interface on the interface reaction zone.

[0036] Optionally, in some embodiments, the surface structure of the phase interface reaction zone can be set, for example, by coating a hydrophobic breathable resin on the surface of the cathode catalyst layer or mixing the cathode catalyst layer with a hydrophobic breathable resin, so that the electrolyte cannot penetrate from the other side of the phase interface reaction zone to one side of the phase interface reaction zone. Since the electrolyte will not be transferred to the outside of the box opening, a gas-liquid-solid interface is formed on the phase interface reaction zone.

[0037] Optionally, in some embodiments, Figures 1 to 5 As shown, the box opening is located on the side of the box; specifically, the left side of the phase interface reaction zone 30 forms a gas-solid critical surface with the air of the box opening 12, and the right side forms a solid-liquid critical surface with the electrolyte in the accommodating chamber 11.

[0038] Optionally, in some embodiments, Figures 6 to 10As shown, the box opening is located on the top of the box; specifically, the box 1 includes an upper box 7 and a lower box 8, the upper box 7 and the lower box 8 enclose a receiving chamber 11, the upper box 7 is provided with a box opening 12 connected to the receiving chamber 11, the upper side of the phase interface reaction zone 30 forms a gas-solid critical surface with the air of the box opening 12, and the lower side forms a solid-liquid critical surface with the electrolyte in the receiving chamber 11. Compared with the embodiment in which the box opening is located on the side of the box, this embodiment can effectively avoid water leakage at the critical surface of the cathode assembly during use.

[0039] like Figures 1 to 10 The static critical surface electrochemical hydrogen peroxide generating device shown in the figure comprises a cathode assembly 3 including a cathode support 31 close to the box opening 12 and a cathode sheet 32 ​​connected to the cathode support 31; the anode assembly 4 includes an anode support 41 away from the box opening 12 and an anode sheet 42 connected to the anode support 41; the cathode support 31 is provided with a cathode support opening 310 communicating with the box opening 12; the cathode sheet 32 ​​is communicated with the box opening 12 through the cathode support opening 310; the anode support 41 is provided with an anode support opening 410 communicating with the accommodating cavity 11; and the hydrophobic air-permeable layer is located on the cathode sheet 32.

[0040] Furthermore, the cathode plate is directly connected to the box opening through the cathode bracket opening, so that oxygen in the air can directly contact the cathode plate, thereby improving oxygen utilization and reaction efficiency, avoiding the problem of limited dissolved oxygen content in traditional devices, and allowing the reaction to proceed faster and more efficiently.

[0041] The anode assembly and cathode assembly of the present invention are separated by a certain distance between the anode assembly and the cathode assembly, which is conducive to the uniform distribution and flow of the electrolyte, and can reduce the problem of uneven distribution of the electrolyte between the cathode and the anode and the problem of excessive local concentration, thereby improving the uniformity and stability of the reaction. The design of the cathode bracket and the anode bracket allows the cathode sheet and the anode sheet to be easily installed and disassembled, which is not only convenient for replacing damaged electrodes, but also helps to clean and maintain the electrodes, thereby extending the service life of the device.

[0042] The cathode support opening enables the gas to better contact one side of the phase interface reaction zone, and the anode support opening enables the electrolyte to better contact the anode sheet. In addition, the design of the cathode support opening facilitates the observation and maintenance of the cathode sheet. During the operation of the device, the operator can directly observe the state of the cathode sheet through the cathode support opening. Optionally, in some embodiments, the operator can observe whether there are bubbles attached to the cathode sheet, whether corrosion occurs, etc. through the cathode support opening. The porous structure of the hydrophobic and breathable layer provides a transmission channel for oxygen, preventing the electrolyte from directly leaking into the electrode. By increasing the gas-liquid contact area, oxygen can reach the electrode surface faster and participate in the reaction, which helps to speed up the reaction rate and improve the efficiency of electrochemical synthesis products.

[0043] In traditional electrochemical devices, the generation and attachment of bubbles will interfere with the flow of electrolyte and the reaction of the electrode. The setting of the hydrophobic and breathable layer can reduce the attachment and accumulation of bubbles on the electrode surface, thereby optimizing the reaction environment and improving the stability and uniformity of the reaction.

[0044] like Figures 1 to 10 In the static critical surface electrochemical hydrogen peroxide generating device shown, the distance between the anode plate 42 and the cathode plate 32 is between 2-50 mm, the anode plate 42 adopts a metal coating substrate, the cathode plate 32 adopts a conductive inert metal material, and the hydrophobic breathable layer includes a cathode catalyst layer and a hydrophobic breathable resin.

[0045] Furthermore, setting the distance between the anode and cathode sheets between 2-50 mm helps optimize the electric field distribution and ensure smooth transmission of electrons and ions during the reaction process. This spacing range avoids the risk of short circuits caused by too close distances and prevents reduced reaction efficiency due to too far distances.

[0046] In addition, the cathode catalyst layer provided on the cathode sheet can significantly improve the rate and efficiency of the electrochemical reaction. The active substances in the cathode catalyst layer can reduce the activation energy of the reaction, thereby accelerating the reaction process and improving the purity and yield of the product. Specifically, the hydrophobic breathable layer can effectively transmit gas through the hydrophobic breathable resin, optimize the distribution of gas on the cathode catalyst layer, and ensure that the reaction gas can evenly contact the active substances in the catalyst layer. At the same time, by preventing the electrolyte from infiltrating, the cathode catalyst layer is prevented from being submerged and failing. The cathode catalyst layer quickly adsorbs and activates the oxygen after it arrives. The two work together to greatly improve the utilization efficiency of oxygen at the cathode, solve the problem that the traditional device limits the reaction process due to the limited amount of dissolved oxygen in water, and allow more oxygen to participate in the cathode reaction, promoting the efficient generation of electrochemical synthesis products.

[0047] Specifically, the electrochemical cathode sheet of the critical surface is formed by coating or mixing a hydrophobic breathable resin on the surface of the cathode catalyst or during the deposition process of the cathode catalyst, and then sintering it twice. Since micro-gaps will be generated during the sintering of the resin, after the addition of the electrolyte, the surface of the cathode catalyst will be in a hydrophobic state, thereby forming a gas-solid-liquid critical surface on the surface, which can greatly improve the generation efficiency of hydrogen peroxide and effectively reduce side reactions. In addition, a metal-coated substrate is used as the anode sheet, which not only has good electrical conductivity, but also can provide stable structural support. The metal-coated substrate has high corrosion resistance and wear resistance, and can maintain stable performance in harsh electrochemical environments. In addition, the cathode sheet is made of a conductive inert metal material, which is not prone to chemical changes during the electrochemical reaction, and therefore can maintain long-term stability and durability.

[0048] like Figures 1 to 10 The static critical surface electrochemical hydrogen peroxide generator shown, the anode plate adopts one of platinum-plated, iridium-tantalum or tin-antimony coated titanium substrates, the coating thickness is 0.1μm-1μm, and the cathode plate adopts one of aluminum, titanium, stainless steel, nickel, platinum, platinum-titanium alloy. Specifically, for the anode plate, platinum has stable chemical properties, is not easily oxidized or corroded, can maintain good catalytic performance for a long time, prolong the service life of the anode, reduce the frequency of anode replacement, improve the continuity and stability of production, the platinum-coated titanium substrate anode plate will not dissolve or produce impurities during the electrolysis process, which helps to improve the purity of the product, and the platinum-coated titanium substrate anode plate can significantly reduce the overpotential of the oxygen evolution reaction, reduce power consumption, thereby reducing production costs and improving energy efficiency.

[0049] Specifically, in the oxygen evolution reaction, iridium can significantly reduce the overpotential required for the reaction, thereby reducing energy consumption. The addition of tantalum can further optimize the structure and performance of the coating, improve the stability and durability of the coating, and the synergistic effect of the two can effectively improve the oxygen evolution catalytic performance of the anode in the process of preparing hydrogen peroxide, thereby improving the efficiency of hydrogen peroxide generation. The iridium-tantalum coated titanium anode is almost insoluble in the electrolyte, has stable dimensions, does not pollute the electrolyte, reduces the frequency of replacement, and reduces the total cost.

[0050] Specifically, the tin antimony oxide layer is uniform and dense, the electrolyte is difficult to penetrate into the titanium surface, and the diffusion of oxygen atoms or ions into the titanium matrix is ​​also blocked, thereby avoiding the formation of titanium dioxide, protecting the titanium substrate, and extending the service life of the anode. Furthermore, the tin antimony oxide bottom layer can also reduce the internal stress of the coating, improve the bonding strength between the coating and the substrate, make the coating more firm and not easy to fall off, thereby ensuring the stability and catalytic performance of the anode during the electrolysis process. In addition, tin antimony oxide has a certain conductivity, which can improve the conductivity of the electrode, reduce the resistance of the electrode, and improve the electrolysis efficiency.

[0051] Specifically, materials such as aluminum, titanium, stainless steel, nickel, and platinum-titanium alloy can resist corrosion from the electrolyte during the electrolysis process, maintain the integrity and stability of the cathode sheet, and extend its service life. Moreover, these materials have good electrical conductivity, which can ensure uniform distribution of current on the cathode sheet, thereby improving electrolysis efficiency. Aluminum has the advantage of low cost, and materials such as titanium, stainless steel, and nickel have high mechanical strength, which can withstand mechanical stress during the electrolysis process and ensure the structural safety of the cathode sheet.

[0052] Specifically, when combined with nanocarbon-based catalysts, nickel can promote the electron transfer process, enhance the cathode's adsorption and activation capabilities for reactants, and help improve the efficiency of hydrogen peroxide production. The nickel surface can form a strong interaction with the nanocarbon-based catalyst through chemical bonding or physical adsorption. This affinity helps the nanocarbon-based catalyst to adhere firmly to the nickel cathode sheet, reducing the shedding and deactivation of the catalyst.

[0053] Specifically, platinum-titanium alloy materials combine the high catalytic activity of platinum with the good chemical stability and mechanical properties of titanium. In the process of preparing hydrogen peroxide at the cathode, the presence of platinum can significantly reduce the activation energy of the reaction, accelerate the reduction reaction of oxygen, and increase the rate of hydrogen peroxide generation. Nanocarbon-based catalysts can further modify the surface active sites of platinum-titanium electrodes and optimize the electron transfer path. At the same time, the platinum-titanium matrix can also provide good support and electron conduction channels for nanocarbon-based catalysts, jointly improving the catalytic performance of the cathode.

[0054] Furthermore, the thickness of the titanium substrate is between 0.5-2mm, the thickness of the coating is 0.1μm-1μm, the thickness of the aluminum cathode sheet is between 0.3-1.5mm, the thickness of the titanium cathode sheet is between 0.5-2.5mm, the thickness of the stainless steel cathode sheet is between 0.3-2mm, the thickness of the nickel cathode sheet is between 0.3-1.2mm, and the thickness of the platinum-titanium cathode sheet is between 0.5-2.0mm.

[0055] like Figures 1 to 10 In the static critical surface electrochemical hydrogen peroxide generator shown, the cathode catalyst layer adopts a nano-carbon-based catalyst, and the hydrophobic air-permeable layer is formed by mixing and sintering a hydrophobic air-permeable resin and the cathode catalyst layer. Specifically, the cathode catalyst deposited on the surface of the cathode sheet is a nano-carbon-based catalyst, such as BN-doped mesoporous carbon, carbon nanotubes, carbon black, nitrogen-doped metal organic framework-derived carbon catalyst, and other highly selective catalysts.

[0056] Specifically, the presence of BN bonds can change the electronic structure of carbon materials, generate more active sites, thereby improving the catalytic activity for oxygen reduction reactions, and is beneficial to promote the two-electron oxygen reduction reaction to produce hydrogen peroxide, thereby improving the selectivity of the product.

[0057] Preparation method of BN-doped mesoporous carbon; M1, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 1,3,5-triisopropylbenzene were dissolved in ethanol, and then boron phenolic resin solution was added, and hydrochloric acid was added to control the pH of the system to 4; Specifically, calculated by mass, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is used as a soft template to form an ordered mesoporous structure, and the dosage is 0.5-2 parts. 1,3,5-triisopropylbenzene is used as an organic solvent and structure directing agent to help form a uniformly dispersed system, and the dosage is 1-3 parts. Ethanol is used as a solvent to dissolve other components and adjust the viscosity of the solution, and the dosage is 50-100 parts. The boron phenolic resin solution adopts TY03 boron phenolic resin to provide a boron source and a carbon source to form BN-doped carbon in a pyrolysis reaction, and the dosage is 2-5 parts of boron phenolic resin to prepare a 20wt% solution. A 0.1M hydrochloric acid solution is used to adjust the pH value to about 4 to promote crosslinking and stabilize the gel structure.

[0058] M2, first evaporate at 25 °C for 24 h, then cross-link at 100 °C for 24 h, and finally heat to 800 °C in a nitrogen atmosphere at a heating rate of 1 °C / min and calcine for 2 h.

[0059] Specifically, carbon nanotubes have a unique one-dimensional nanostructure and excellent electrical properties, can achieve rapid conduction of electrons, can effectively reduce the resistance of the electrode, improve the kinetics of the electrocatalytic reaction, and are beneficial to increasing the generation rate of hydrogen peroxide.

[0060] Specifically, carbon black has high conductivity, which can promote the transfer of electrons on the electrode surface and improve the efficiency of electrochemical reactions. It also has good dispersibility in the solution and can be evenly distributed on the surface of the cathode sheet, giving full play to its catalytic effect and making the reaction proceed more evenly.

[0061] Specifically, metal-organic framework materials have abundant metal centers and organic ligands. During the pyrolysis derivatization process, metal atoms can serve as active sites. At the same time, the doping of nitrogen atoms can also introduce additional active sites, which greatly improves the active site density of the catalyst and enhances the catalytic activity for the oxygen reduction reaction, which is beneficial to the efficient generation of hydrogen peroxide. After pyrolysis derivatization, a stable chemical bond or interaction is formed between the carbon material and the metal species, so that the catalyst has good structural stability and chemical stability during the electrochemical reaction, and can maintain a high catalytic performance for a long time, reduce the deactivation of the catalyst, and improve the service life of the catalyst.

[0062] Method for preparing metal organic framework derived carbon catalyst; N1. React cobalt nitrate with 2-methylimidazole in methanol to generate nanocrystals; methanol is used as a reaction solvent to ensure a sufficient amount to dissolve the reactants. Specifically, cobalt nitrate is dissolved in methanol and stirred evenly at room temperature to form a transparent solution. The stirring speed is 300-600 rpm. The concentration of the cobalt nitrate solution is configured to be between 0.01-0.1 mol / L. The molar ratio of cobalt nitrate to 2-methylimidazole is between 1:2 and 1:4. 2-methylimidazole ensures that the metal ions can fully coordinate with the organic ligands to form a metal organic framework structure. The reaction temperature is between 25°C and 120°C, and the reaction time is 12 hours to 48 hours to obtain ZIF-67 nanocrystals.

[0063] N2, pyrolyze the synthesized nanocrystals in an inert atmosphere to obtain a metal organic framework derived carbon catalyst. Nitrogen was used as the inert atmosphere, and the gas flow rate was controlled at 30-100 mL / min. Specifically, the pyrolysis temperature is between 800°C and 1000°C, the heating rate is usually controlled at 1-10°C / min, and the pyrolysis time is 2 hours to 5 hours. The organic components of ZIF-67 nanocrystals are fully decomposed and carbonized, while the cobalt element is reduced and dispersed on the carbon substrate to form a derived carbon composite electrocatalyst with good electrochemical properties. Some nitrogen atoms in 2-methylimidazole will be fixed on the carbon skeleton. This nitrogen doping can change the electronic structure of the carbon material and produce more active sites, which is beneficial to improve the performance of the catalyst in the preparation of electrochemical hydrogen peroxide.

[0064] Specifically, the hydrophobic and breathable resin is polytetrafluoroethylene resin. The polytetrafluoroethylene resin has certain electrical conductivity, good hydrophobicity and air permeability. Specifically, the preparation method of the polytetrafluoroethylene resin is: P1. Add 500-700 parts of deionized water into the reaction container, and then add 0.005-0.05 parts of peroxysuccinic acid, 0.5-5 parts of perfluorobutylethylene, 0.5-5 parts of ammonium perfluoropolyether carboxylate, 20-50 parts of saturated hydrocarbons with carbon atoms greater than 12, 10-30 parts of fillers, and 0.5-2 parts of succinic acid in sequence; stir well; Specifically, the filler is hydrophobic silica and carbon nanotubes; polytetrafluoroethylene itself has strong hydrophobicity, and its molecular chain is composed of carbon-fluorine bonds. The electronegativity of fluorine atoms is large, which makes the intermolecular force weak and the surface energy extremely low, thus showing excellent hydrophobicity. There are a large number of silanol groups on the surface of hydrophobic silica, which can interact with polytetrafluoroethylene molecular chains, and its own hydrophobic groups also increase the overall hydrophobicity; carbon nanotubes can improve the conductivity of the coating without significantly affecting its hydrophobicity and air permeability. It has a large specific surface area and a special one-dimensional nanostructure. The carbon atoms on its surface will also interact with the polytetrafluoroethylene molecular chains to improve the hydrophobicity of the resin. Good hydrophobicity can make the generated hydrogen peroxide quickly and effectively leave the electrode interface, prevent hydrogen peroxide from excessively accumulating on the electrode surface, and is conducive to improving the utilization rate, selectivity and stability of the electrode. Polytetrafluoroethylene resin is composed of interconnected nodules and fibrils to form a three-dimensional network, forming a porous structure, which allows gases such as air to pass through, thus having a certain air permeability.

[0065] Specifically, peroxysuccinic acid as an initiator can decompose to generate free radicals, which can attack the double bonds in the tetrafluoroethylene monomer, causing it to open and undergo a chain polymerization reaction with other monomers, thereby promoting the formation of polytetrafluoroethylene.

[0066] Specifically, perfluorobutylethylene mainly plays a modifying role, and its molecular structure contains carbon-carbon double bonds and perfluorobutyl groups. The presence of perfluorobutyl makes the compound have excellent chemical stability, low surface energy and hydrophobicity. It can be copolymerized with tetrafluoroethylene monomer to introduce perfluorobutylethylene units with special properties into the molecular chain of polytetrafluoroethylene. The addition of perfluorobutylethylene can improve the processing properties of polytetrafluoroethylene and make it easier to form.

[0067] Specifically, perfluoropolyether ammonium carboxylate is mainly composed of perfluoropolyether segments and ammonium carboxylate groups. Due to the hydrophobicity and low surface energy of polytetrafluoroethylene itself, agglomeration is easy to occur. Perfluoropolyether ammonium carboxylate can be adsorbed on the surface of polytetrafluoroethylene particles. Its perfluoropolyether segments have good affinity with polytetrafluoroethylene particles, while the ammonium carboxylate groups extend into the aqueous solution. This reduces the mutual attraction between polytetrafluoroethylene particles, allowing them to be evenly dispersed in water to form a stable dispersion system. The appropriate dosage can ensure a good dispersion effect, which is conducive to the polymerization reaction in a uniform environment, thereby obtaining a polytetrafluoroethylene dispersion resin with stable performance and uniform quality.

[0068] Specifically, the saturated hydrocarbon with a carbon number greater than 12 is paraffin. As a stabilizer, paraffin can form a protective film around the polytetrafluoroethylene molecular chain, which plays an isolation and buffering role, reducing the damage of external factors to the polytetrafluoroethylene molecular chain. At the same time, it can also improve the flexibility of the polytetrafluoroethylene dispersion resin and reduce its viscosity.

[0069] Specifically, succinic acid is used to adjust the pH value of the reaction system between 4 and 6 to ensure the smooth progress of the polymerization reaction. If the pH is too low, the ionization of the carboxylate group may be inhibited, resulting in a decrease in the hydrophilicity of the dispersant, which is not conducive to the dispersion of polytetrafluoroethylene particles; if the pH is too high, the molecular structure of the dispersant may change, which also affects its dispersion effect.

[0070] P2. Introduce nitrogen, control the pressure at 1.5-3Mpa, the temperature at 70-105°C, add 200-400 parts of gas-phase tetrafluoroethylene monomer, and stir at a speed of 50-70 rpm until the solid content of the emulsion reaches 30%, then stop stirring, recover the gas-phase monomer, evacuate, and discharge; introduce nitrogen to make the oxygen content in the reactor ≤30ppm to exclude oxygen in the system and avoid adverse effects of oxygen on the polymerization reaction.

[0071] P3. Collect the obtained polytetrafluoroethylene polymer solution, and obtain polytetrafluoroethylene dispersion resin through condensation, washing and drying processes. Specifically, add saturated sodium chloride solution, control the stirring speed to 30-50 rpm, the polymer solution gradually becomes turbid, and the polytetrafluoroethylene particles begin to condense into larger agglomerates, rinse with deionized water for 3-5 times, dry in a blast drying oven at 100-130° C. for about 10-15 hours, and the obtained polytetrafluoroethylene dispersion resin can be packaged and stored.

[0072] like Figures 1 to 10 In the static critical surface electrochemical hydrogen peroxide generating device shown, the box body 1 is provided with a first limiting frame 5 for fixing the cathode support 31, and a second limiting frame 6 for fixing the anode support 41, the cathode support 31 and the anode support 41 are arranged opposite to each other, the cathode sheet 32 ​​and the anode sheet 42 are arranged opposite to each other, and the second limiting frame 6 is provided with a plurality of limiting grooves 60 for the anode support 41 to extend into, and the plurality of limiting grooves 60 are arranged at intervals. Furthermore, the cathode support and the anode support are fixed by the first limiting frame and the second limiting frame respectively, so that the structure of the entire electrochemical device is more stable, which helps to prevent the electrode from shaking or shifting due to factors such as electrolyte flow and bubble generation during the reaction process, thereby ensuring the continuity and stability of the reaction.

[0073] Specifically, the cathode support and the anode support can be accurately positioned at predetermined positions of the box through the first limit frame and the second limit frame respectively, ensuring that the spacing between the electrodes remains consistent during the reaction. This consistency helps to optimize the conditions of the electrochemical reaction, such as current density, electric field distribution, etc., thereby improving the reaction efficiency and product quality.

[0074] Furthermore, multiple limiting grooves are arranged at intervals, so that the anode support can be flexibly arranged at different positions in the electrochemical device. The operator can adjust the distance between the cathode support and the anode support as needed. This flexibility helps to optimize the electric field distribution between the anode and the cathode, ensure the smooth transmission of electrons and ions during the reaction process, and thus improve the rate and efficiency of the electrochemical reaction.

[0075] Alternatively, if Figures 1 to 5 As shown, when the box opening is located at the side of the box, the limiting groove can extend in the horizontal direction, such as Figures 6 to 10 As shown, when the box opening is located on the upper side of the box, it can also extend in the vertical direction. Specifically, the setting of the limit groove simplifies the installation process of the anode bracket. The operator only needs to align the anode bracket with the limit groove and insert it from top to bottom or horizontally. It not only saves installation time, but also reduces the installation difficulty and cost, and improves the maintenance efficiency and flexibility of the electrochemical device. The limit groove extending in the vertical direction helps to maintain the stability of the anode bracket in the vertical direction, avoids the uneven reaction caused by shaking or tilting, helps to improve the purity and yield of the product, reduces the occurrence of side reactions, and avoids the risks of short circuit or equipment damage caused by the anode bracket falling off.

[0076] Optionally, in some embodiments, Figures 1 to 5 As shown, when the box opening is located on the side of the box, the first limit frame 5 includes a first left limit bracket 51 and a first right limit bracket 52 respectively arranged on both sides of the box opening 12, and the second limit frame 6 includes a second left limit bracket 61 and a second right limit bracket 62 respectively arranged on both sides of the box opening 12, the first left limit bracket 51 and the first right limit bracket 52 are arranged opposite to each other, the second left limit bracket 61 and the second right limit bracket 62 are arranged opposite to each other, and the cathode plate 32 and the anode plate 42 are arranged opposite to each other.

[0077] Furthermore, the first left limit bracket and the first right limit bracket are relatively arranged to fix the cathode bracket, and the second left limit bracket and the second right limit bracket are relatively arranged to fix the anode bracket. This symmetrical structural design allows the cathode assembly and the anode assembly to be firmly fixed in the box. It can prevent the displacement of the cathode sheet and the anode sheet, ensure the structural stability of the device, and help ensure that the cathode sheet and the anode sheet are relatively arranged to maintain a uniform and fixed distance between the two, thereby forming a uniform electric field distribution. This uniform electric field distribution is conducive to the transmission of electrons and ions, thereby improving the rate and efficiency of the electrochemical reaction.

[0078] Specifically, in the electrolyte solution, the uniform electric field promotes the migration of cations to the cathode and anions to the anode in a more orderly and uniform manner. For cathode reactions that require the consumption of dissolved oxygen, this uniform electric field and ion migration environment is conducive to the uniform diffusion of oxygen in the electrolyte to the cathode surface, and also enables the reaction products to diffuse away from the electrode surface in a timely manner, avoiding the situation of excessively high or low local concentrations, thereby optimizing the reaction performance and improving the efficiency and quality of product generation.

[0079] Optionally, in some embodiments, Figures 6 to 10 As shown, when the box opening is located on the upper side of the box, the upper box 7 is provided with a supporting portion 71, and the supporting portion 71 is provided with a supporting portion opening 72 for the cathode support 31 and the anode support 41 to extend into, a first limiting frame 5 for fixing the cathode support 31, and a second limiting frame 6 for fixing the anode support 41, the cathode support 31 and the anode support 41 are arranged opposite to each other, the first limiting frame 5 and the second limiting frame 6 are arranged in parallel, and the cathode sheet 32 ​​and the anode sheet 42 are arranged opposite to and in parallel.

[0080] Specifically, the supporting part can support the cathode support and the anode support. When the cathode support and the anode support need to be installed or removed, the cathode support can be driven from the opening of the supporting part to be separated from or connected to the first limiting frame, or the anode support can be driven from the opening of the supporting part to be separated from or connected to the second limiting frame. The first limiting frame is located on the upper side of the second limiting frame.

[0081] Alternatively, if Figures 6 to 10 As shown, the upper box 7 is provided with a handle 75 and an upper box positioning portion 70, the lower box 8 is provided with a lower box limiting portion 80 matched with the upper box positioning portion 70, and a water inlet 81 and a water outlet 82 respectively connected to the accommodating chamber 11, the accommodating chamber 11 is provided with a drainage portion 111 connected to the water inlet 81 and / or the water outlet 82, and the drainage portion 111 is provided with a drainage channel connected to the accommodating chamber 11. Optionally, in some embodiments, the handle provided on the upper box can facilitate operators to lift or place the upper box.

[0082] Optionally, in some embodiments, the position of the upper box can be further fixed by the cooperation of the upper box positioning part and the lower box limiting part. Specifically, in some embodiments, the upper box positioning part is a protrusion extending toward the accommodating cavity, and the lower box limiting part is a plane abutting against the lower side of the upper box. In other embodiments, the upper box positioning part is a protrusion extending toward the accommodating cavity, and the lower box limiting part is a matching groove.

[0083] Optionally, in some embodiments, the drainage portion is provided so that the electrolyte can enter or leave the accommodating chamber along the drainage channel, so that the flow of the solution is more uniform. Specifically, the drainage portion drives the liquid to flow in the vertical direction, and the water inlet and the water outlet are arranged relative to each other so that the movement stroke of the electrolyte is increased, and the electrolyte will not leave the accommodating chamber immediately after moving from the water inlet to the accommodating chamber.

[0084] Optionally, a water inlet pipe connected to the water inlet and an overflow pipe connected to the water outlet are opened on the side of the lower box body. Reaction water in the external environment can be flexibly drawn into the accommodating chamber through the water inlet pipe. After the reaction is completed, the hydrogen peroxide solution in the lower box body can be pumped out through the overflow port by an external water pump or a built-in water pump to achieve flexible preparation of hydrogen peroxide.

[0085] like Figures 1 to 10 In the static critical surface electrochemical hydrogen peroxide generating device shown, the cathode support 31 includes a first cathode support 311, a second cathode support 312, and a cathode support accommodating cavity 313 located between the first cathode support 311 and the second cathode support 312, and the cathode sheet 32 ​​is located in the cathode support accommodating cavity 313; the anode support 41 includes a first anode support 411, a second anode support 412, and an anode support accommodating cavity 413 located between the first anode support 411 and the second anode support 412, and the anode sheet 42 is located in the anode support accommodating cavity 413; the cathode support opening 310 is respectively provided in the first cathode support 311 and the second cathode support 312, and the anode support opening 410 is respectively provided in the first anode support 411 and the second anode support 412.

[0086] Furthermore, the cathode bracket and the anode bracket adopt a layered structure, and the first cathode bracket, the second cathode bracket and the first anode bracket, the second anode bracket make the position of the corresponding electrode sheet in its corresponding accommodating cavity more stable. The cathode sheet is located in the cathode bracket accommodating cavity, and the anode sheet is located in the anode bracket accommodating cavity. This structure provides good physical protection for the electrode sheet. It prevents the surface of the electrode sheet from being scratched or deformed due to accidental collision, thereby extending the service life of the electrode sheet. The cathode bracket and the anode bracket can limit the movement of the corresponding electrode sheet in the plane, ensuring that the electrode sheet always remains in the appropriate position during the reaction process, which is conducive to maintaining a stable electric field distribution and a uniform reaction environment. In the presence of liquid flow or slight vibration, the electrode sheet can also stably perform electrochemical reactions.

[0087] In addition, when the electrode sheet needs to be replaced, the new electrode sheet can be directly taken out or put into the cathode support accommodating cavity or the anode support accommodating cavity without large-scale disassembly of the entire device. At the same time, the type, size or number of the electrode sheet can be flexibly adjusted in the cathode support accommodating cavity or the anode support accommodating cavity according to different reaction requirements, thereby improving the adaptability and scalability of the device.

[0088] The cathode support openings are respectively arranged on the first cathode support and the second cathode support, and the anode support openings are respectively arranged on the first anode support and the second anode support. Such an arrangement enables the electrolyte to fully contact the electrode sheet without any obstruction, so that the distance between the cathode sheet and the anode sheet remains consistent and the electric field distribution is more uniform.

[0089] like Figures 1 to 10 In the static critical surface electrochemical hydrogen peroxide generating device shown, the first cathode support 311 is provided with a cathode support clamping portion 3111, the second cathode support 312 is provided with a cathode support connecting portion 3121 which is matched and connected with the cathode support clamping portion 3111, the first anode support 411 is provided with an anode support clamping portion 4111, the second anode support 412 is provided with an anode support connecting portion 4121 which is matched and connected with the anode support clamping portion 4111, the cathode support 31 is provided with a cathode support connecting groove 33 for extending one end of the cathode sheet 32 ​​to be connected to an external power supply, and the anode support 41 is provided with an anode support connecting groove 43 for extending one end of the anode sheet 42 to be connected to an external power supply.

[0090] Furthermore, by the matching connection between the cathode bracket clamping part and the cathode bracket connecting part, and the anode bracket clamping part and the anode bracket connecting part, this arrangement not only saves assembly time, but also reduces assembly difficulty and cost. At the same time, this arrangement also enhances the structural stability of the cathode bracket and the anode bracket, and helps prevent the bracket from shaking or shifting due to factors such as electrolyte flow and bubble generation during the reaction process, thereby ensuring the stable operation of the electrochemical device.

[0091] In addition, the design of the cathode support connecting groove and the anode support connecting groove allows one end of the cathode plate and the anode plate to be easily extended to connect to an external power source. This arrangement simplifies the connection process, reduces the connection difficulty and cost, and this stable connection helps to ensure the continuity and stability of the electrochemical reaction, thereby improving the operating efficiency and reliability of the device.

[0092] Optionally, in some embodiments, the cathode support engaging portion may be a protrusion, the cathode support connecting portion may be a groove, the anode support engaging portion may be a protrusion, and the anode support connecting portion may be a groove.

[0093] Optionally, in some embodiments, the cathode support engaging portion may be a groove, the cathode support connecting portion may be a protrusion, the anode support engaging portion may be a groove, and the anode support connecting portion may be a protrusion.

[0094] Optionally, in some embodiments, Figures 6 to 10 As shown, the upper box body 7 is provided with a wire groove 74 for the line to pass through, and the wire groove 74 is located on the same side as the cathode support connection groove 33 and the anode support connection groove 43. The position of the wire groove allows the line to pass through the upper box body in an orderly manner in the shortest stroke, which is convenient for operators to install and disassemble.

[0095] like Figures 1 to 10 In the static critical surface electrochemical hydrogen peroxide generating device shown, the box body 1 is provided with a box body positioning portion 13 arranged along the peripheral side of the box body opening 12, and the cathode support 31 is provided with a cathode limiting portion 314 abutting against the box body positioning portion 13. Furthermore, the cooperation between the box body positioning portion and the cathode limiting portion enables the cathode support to maintain the same position and angle each time it is installed, and this consistency helps to optimize the electric field distribution, ensure the smooth transmission of electrons and ions during the reaction process, and thus improve the rate and efficiency of the electrochemical reaction.

[0096] Additionally, by firmly fixing the cathode support to the housing, this arrangement enhances the structural strength of the entire electrochemical device, helps resist external stress and vibration, and improves the durability and reliability of the device.

[0097] Optionally, in some embodiments, the box positioning portion may be a protrusion extending along the peripheral side of the box opening toward the cathode support, and the cathode limiting portion may be a side wall of the first cathode support that is attached to the box positioning portion.

[0098] Optionally, in some embodiments, the cathode limit portion may be a protrusion extending along the circumference of the cathode support opening toward the box opening, and the box positioning portion may be arranged on the inner wall of the circumference of the box opening and attached to the cathode limit portion.

[0099] Furthermore, a method for preparing hydrogen peroxide using a stationary critical surface electrochemical hydrogen peroxide generator comprises the stationary critical surface electrochemical hydrogen peroxide generator as described above, and the preparation method comprises the following steps: S1, cathode assembly 3 and anode assembly 4 are respectively fixed in the accommodating cavity 11, and one side of the cathode assembly 3 is connected to the box opening 12; S2, cathode assembly 3 and anode assembly 4 are electrically connected to an external power supply through wires, electrolyte is added to water tank 1, one side of the phase interface reaction zone 30 forms a gas-solid critical surface with the air of the box opening 12, and the electrolyte on the other side of the phase interface reaction zone 30 forms a solid-liquid critical surface; S3. After power is input, the cathode assembly 3 forms a gas-solid-liquid critical surface, the oxygen generated by the anode assembly 4 reaches the solid-liquid critical surface of the adjacent phase interface reaction zone 30, and the oxygen in the air enters the cathode assembly 3 through the gas-solid critical surface of the adjacent phase interface reaction zone 30 for replenishment, thereby producing hydrogen peroxide.

[0100] The present invention provides a new static critical surface electrochemical hydrogen peroxide generation device with compact structure, static type, no diaphragm, modularization and adjustable power, which can realize the continuous preparation of high-concentration hydrogen peroxide. Among them, based on the critical hydrogen peroxide electrochemical reaction device, the cathode component can be free from the restriction of dissolved oxygen in water, and the efficiency and equilibrium concentration of electrochemical synthesis of hydrogen peroxide can be significantly improved when powered. Its device structure is mainly designed as a special generator, and its core part includes an anode sheet, a cathode sheet and a phase interface reaction zone. Among them, the phase interface reaction zone is constructed by coating the surface of the deposited cathode catalyst with a hydrophobic breathable resin, or mixing a hydrophobic breathable resin with a cathode catalyst through a special structural design, so that a stable phase interface is formed between the electrolyte and the gas or other gas phases participating in the reaction on the surface of the cathode sheet. Through this special phase interface, the gas-cathode catalyst-electrolyte can be fully contacted at a microscale, so that the reaction cathode can obtain sufficient oxygen supply, thereby increasing the yield of hydrogen peroxide.

[0101] Optionally, in some embodiments, the anode material is preferably a metal oxide with strong corrosion resistance and high catalytic oxidation activity, a conductive inert metal material, such as platinum titanium, ruthenium iridium oxide, tin antimony oxide, boron-doped diamond, graphene coating material, etc. The cathode material is preferably a non-metallic material with high two-electron selectivity and a doped metal material, such as carbon nanotubes, porous graphite plates, carbon black, carbon fiber, BN-doped mesoporous carbon, platinum black, etc., using the high specific surface area and good conductivity of porous materials to improve the oxygen contact effect and the oxygen reduction reaction efficiency.

[0102] The electrolyte for the reaction can be tap water, river water, rain water and other common water bodies in life. The water in the electrolyte combines with the oxygen exposed on the critical surface to prepare hydrogen peroxide, which has the advantages of easy availability of raw materials and environmental protection, clean and efficient production process, flexibility and sustainability, and broad application prospects.

[0103] A small amount of electrolyte may also be added to the electrolyte, including but not limited to NaHCO 3 ,NaCO 3 ,KHCO 3 ,K 2 CO 3 ,Na 2 SO 4 , H 2 SO 4 The electrochemical generating device has no special requirements on the conductivity and pH of the electrolyte used therein.

[0104] Among them, the preparation method of hydrogen peroxide can be multi-dimensionally controlled according to different application scenarios and needs. Including but not limited to adjusting the electrode voltage, electrolyte composition and concentration, the area and properties of the phase interface, etc. For example, when low-concentration hydrogen peroxide is required, the electrode voltage can be reduced and the electrolyte concentration can be reduced; when preparing high-concentration hydrogen peroxide, the current density can be increased, the electrolyte concentration can be increased, and the electrode voltage can be adjusted to the optimal value to achieve the purpose of controlling the balance between reaction performance and economy.

[0105] The present invention also provides the application of a stationary critical surface electrochemical hydrogen peroxide generator. The prepared hydrogen peroxide is used for water purification, environmental disinfection, and food processing. The high-concentration hydrogen peroxide solution produced by the present invention can be directly used in treatment processes such as sterilization, organic matter oxidation, and pollution control. Since the concentration of hydrogen peroxide is greatly increased and the volume of the device itself is not significantly enlarged, it shows a more excellent effect compared to traditional electrochemical methods and can greatly broaden the application field.

[0106] Embodiment 1 like Figures 1 to 5The static critical surface electrochemical hydrogen peroxide generating device shown comprises a box body 1, wherein the box body 1 is provided with a containing cavity 11, a box body opening 12 communicating with the containing cavity 11 is provided on the side of the box body 1, a cathode assembly 3 located in the containing cavity 11 and close to the box body opening 12, and an anode assembly 4 located in the containing cavity 11 and away from the box body opening 12, wherein the cathode assembly 3 is provided with a phase interface reaction zone 30 communicating with the box body opening 12, wherein the phase interface reaction zone 30 forms a gas-solid critical surface with the air of the box body opening 12 on the left side, and forms a solid-liquid critical surface with the electrolyte of the containing cavity 11 on the right side. The present invention forms a gas-solid critical surface with the left side of the cathode assembly 3 and the air in the box opening 12 by setting a phase interface reaction zone 30, thereby increasing the contact area between the cathode and oxygen in the air, so that the oxygen can be more fully utilized by the cathode, providing a continuous oxygen supply for the cathode reaction. The right side of the phase interface reaction zone 30 forms a solid-liquid critical surface with the electrolyte in the accommodating chamber 11, so that the reaction can continue, thereby improving the efficiency and equilibrium concentration of the electrochemical synthesis product and ensuring the continuous preparation of high-concentration products.

[0107] The cathode assembly 3 includes a cathode support 31 close to the box opening 12 and a cathode plate 32 connected to the cathode support 31. The anode assembly 4 includes an anode support 41 away from the box opening 12 and an anode plate 42 connected to the anode support 41. The cathode support 31 is provided with a cathode support opening 310 connected to the box opening 12. The cathode plate 32 is connected to the box opening 12 through the cathode support opening 310. The anode support 41 is provided with an anode support opening 410 connected to the accommodating cavity 11.

[0108] The cathode sheet 32 ​​is provided with a hydrophobic and breathable layer, and the phase interface reaction zone 30 is located in the hydrophobic and breathable layer. The box body 1 is provided with a first limiting frame 5 for fixing the cathode support 31, and a second limiting frame 6 for fixing the anode support 41, and the cathode support 31 and the anode support 41 are arranged opposite to each other. The second limiting frame 6 is provided with a plurality of limiting grooves 60 for the anode support 41 to extend into, and the plurality of limiting grooves 60 are arranged at intervals, and the limiting grooves 60 extend in the vertical direction.

[0109] The first limiting frame 5 includes a first left limiting frame 51 and a first right limiting frame 52 respectively arranged on both sides of the box opening 12, and the second limiting frame 6 includes a second left limiting frame 61 and a second right limiting frame 62 respectively arranged on both sides of the box opening 12, the first left limiting frame 51 and the first right limiting frame 52 are arranged opposite to each other, the second left limiting frame 61 and the second right limiting frame 62 are arranged opposite to each other, and the cathode plate 32 and the anode plate 42 are arranged opposite to each other.

[0110] The cathode support 31 includes a first cathode support 311, a second cathode support 312, and a cathode support accommodating cavity 313 located between the first cathode support 311 and the second cathode support 312, and the cathode sheet 32 ​​is located in the cathode support accommodating cavity 313. The anode support 41 includes a first anode support 411, a second anode support 412, and an anode support accommodating cavity 413 located between the first anode support 411 and the second anode support 412, and the anode sheet 42 is located in the anode support accommodating cavity 413. The cathode support opening 310 is respectively provided in the first cathode support 311 and the second cathode support 312, and the anode support opening 410 is respectively provided in the first anode support 411 and the second anode support 412.

[0111] The first cathode support 311 is provided with a cathode support clamping portion 3111, the second cathode support 312 is provided with a cathode support connecting portion 3121 which cooperates with the cathode support clamping portion 3111, the first anode support 411 is provided with an anode support clamping portion 4111, the second anode support 412 is provided with an anode support connecting portion 4121 which cooperates with the anode support clamping portion 4111, the cathode support 31 is provided with a cathode support connecting groove 33 for one end of the cathode sheet 32 ​​to extend and connect to an external power supply, and the anode support 41 is provided with an anode support connecting groove 43 for one end of the anode sheet 42 to extend and connect to an external power supply.

[0112] The cathode support clamping portion 3111 is a protrusion, the cathode support connecting portion 3121 is a groove, the anode support clamping portion 4111 is a protrusion, and the anode support connecting portion 4121 is a groove.

[0113] The box body 1 is provided with a box body positioning portion 13 arranged along the circumference of the box body opening 12 , and the cathode support 31 is provided with a cathode limiting portion 314 abutting against the box body positioning portion 13 .

[0114] The box positioning portion 13 is a protrusion extending along the peripheral side of the box opening 12 toward the cathode support 31 , and the cathode limiting portion 314 is a side wall of the first cathode support 311 that is attached to the box positioning portion 13 .

[0115] The distance between the anode sheet 42 and the cathode sheet 32 ​​is 2 mm. The anode sheet 42 adopts a metal coating substrate. The cathode sheet 32 ​​adopts a conductive inert metal material. The cathode sheet 32 ​​is provided with a cathode catalyst layer. The hydrophobic air-permeable layer is connected to the surface of the cathode catalyst layer. The anode sheet adopts a platinum-coated titanium substrate with a coating thickness of 0.1 μm. The cathode sheet adopts stainless steel material. The cathode catalyst deposited on the surface of the cathode sheet is carbon black.

[0116] Embodiment 2 Embodiment 2 Based on Embodiment 1, the following implementation methods are also provided: A method for preparing hydrogen peroxide by a stationary critical surface electrochemical hydrogen peroxide generator comprises the stationary critical surface electrochemical hydrogen peroxide generator as described above, and the preparation method comprises the following steps: S1, cathode assembly 3 and anode assembly 4 are respectively fixed in the accommodating cavity 11, and the left side of the cathode assembly 3 is connected to the box opening 12; S2, cathode assembly 3 and anode assembly 4 are electrically connected to an external power supply through wires, electrolyte is added to water tank 1, the air on the left side of the phase interface reaction zone 30 and the box opening 12 form a gas-solid critical surface, and the electrolyte on the right side of the phase interface reaction zone 30 forms a solid-liquid critical surface; S3. After power is input, the cathode assembly 3 forms a gas-solid-liquid critical surface, the oxygen generated by the anode assembly 4 reaches the solid-liquid critical surface of the adjacent phase interface reaction zone 30, and the oxygen in the air enters the cathode assembly 3 through the gas-solid critical surface of the adjacent phase interface reaction zone 30 for replenishment, thereby producing hydrogen peroxide.

[0117] The process of hydrogen peroxide generation is as follows: after electricity is input, when a specific volume of electrolyte is added to the reaction water tank, the electrolyte forms a gas-solid-liquid critical surface on the cathode surface. Under the action of the cathode catalyst, the two-electron oxygen reduction reaction takes place on the cathode surface, and the generated hydrogen peroxide diffuses rapidly in the electrolyte. At the same time, through the critical surface, the oxygen consumed on the cathode surface can be replenished from the air. Since the oxygen content in the air is much greater than the dissolved oxygen in the water, the production of hydrogen peroxide during the reaction can be greatly increased.

[0118] In specific applications, the critical surface hydrogen peroxide generating device involved in the present invention, when powered on, the internal resistance of the electrochemical generating device will change when there is liquid and no liquid inside. In engineering applications, the current value or resistance value of the acquisition device can be used to judge the operating state and water level of the electrochemical device based on the value, thereby realizing functions such as waterless detection.

[0119] In specific applications, the critical surface hydrogen peroxide generating device designed by the present invention can adopt constant voltage power supply and constant current power supply according to actual needs. By setting the external power supply parameters, the flexible preparation of hydrogen peroxide can be achieved, and the economy and performance of the reaction device can be optimized in the appropriate voltage and current range.

[0120] In actual application scenarios, when the device is used to prepare hydrogen peroxide, in order to avoid the particles in domestic water or the scale produced by calcium and magnesium ions under the action of the electric field to reduce the reaction effect, it is preferred to use water samples softened by common filters in life and add a small amount of electrolyte to improve the reaction effect.

[0121] Embodiment 3 The difference between Example 3 and Example 1 is that the distance between the anode sheet 42 and the cathode sheet 32 ​​is 20 mm, the anode sheet 42 adopts a metal coating substrate, the cathode sheet 32 ​​adopts a conductive inert metal material, the cathode sheet is deposited with a cathode catalyst layer, and a hydrophobic breathable resin is coated on the surface of the cathode catalyst layer. The anode sheet adopts an iridium-tantalum coated titanium substrate with a coating thickness of 0.5 μm. The cathode sheet adopts a platinum-titanium material. The cathode catalyst deposited on the surface of the cathode sheet is BN-doped mesoporous carbon.

[0122] Preparation method of BN-doped mesoporous carbon; M1, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and 1,3,5-triisopropylbenzene were dissolved in ethanol, and then boron phenolic resin solution was added, and hydrochloric acid was added to control the pH of the system to 4; Specifically, calculated by mass, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is used as a soft template to form an ordered mesoporous structure, and the dosage is 0.5-2 parts. 1,3,5-triisopropylbenzene is used as an organic solvent and structure directing agent to help form a uniformly dispersed system, and the dosage is 1-3 parts. Ethanol is used as a solvent to dissolve other components and adjust the viscosity of the solution, and the dosage is 50-100 parts. The boron phenolic resin solution adopts TY03 boron phenolic resin to provide a boron source and a carbon source to form BN-doped carbon in a pyrolysis reaction, and the dosage is 2-5 parts of boron phenolic resin to prepare a 20wt% solution. A 0.1M hydrochloric acid solution is used to adjust the pH value to about 4 to promote crosslinking and stabilize the gel structure.

[0123] M2, first evaporate at 25 °C for 24 h, then cross-link at 100 °C for 24 h, and finally heat to 800 °C in a nitrogen atmosphere at a heating rate of 1 °C / min and calcine for 2 h.

[0124] The hydrophobic and breathable layer is polytetrafluoroethylene resin. The hydrophobic and breathable resin is coated on the surface of the cathode catalyst layer. The preparation method of the polytetrafluoroethylene resin is as follows: P1, add 500 parts of peroxysuccinic acid, 0.005 parts of perfluorobutylethylene, 0.5 parts of ammonium perfluoropolyether carboxylate, 20 parts of paraffin, 4 parts of German Wacker HDK H15 hydrophobic silica and 6 parts of carbon nanotubes, and 0.5 parts of succinic acid to the reaction container in sequence, and stir; P2, introduce nitrogen, control the pressure at 2.0 MPa, temperature at 70-105°C, add 200 parts of gaseous tetrafluoroethylene monomer, stir at 50 rpm, until the solid content of the emulsion reaches 30%, stop stirring, recover the gaseous monomer, evacuate, and discharge; P3. Collect the obtained polytetrafluoroethylene polymerization liquid, add saturated sodium chloride solution, control the stirring speed at 30 rpm, the polymerization liquid gradually becomes turbid, and the polytetrafluoroethylene particles begin to condense into larger agglomerates. Rinse with deionized water for 3 times, and dry in a 100°C forced air drying oven for about 15 hours. The obtained polytetrafluoroethylene dispersion resin can be packaged and stored.

[0125] Embodiment 3 Based on Embodiment 1, the following implementation methods are also provided: Example 3 tests the actual performance of the critical surface hydrogen peroxide generator, wherein the power supply voltage of the stationary critical surface hydrogen peroxide generator is 12V, the anode area is the same as the cathode area, and the electrode spacing is 20mm. Experimental plan: 2L of pure water is added to a beaker, 14.2g of sodium sulfate is added thereto, and a 0.05M sodium sulfate solution is prepared. After stirring evenly, pour it into the reaction water tank, connect the cathode and cathode power supplies in the reaction water tank, and test the hydrogen peroxide concentration in the water tank within 60min. Under the condition of 12V direct current, prepare a hydrogen peroxide solution, take samples 6 times continuously according to the preset time interval, and continue to test for 60min to determine the cumulative concentration of hydrogen peroxide in the water body.

[0126] like Fig.11 As shown, when using 2L 0.05M sodium sulfate solution for reaction, the concentration of hydrogen peroxide accumulated in 60 minutes by the critical surface hydrogen peroxide electrochemical generator of the present invention can reach 700ppm, indicating that the electrochemical generator can realize the preparation of high-concentration hydrogen peroxide solution and has good performance.

[0127] Embodiment 4 Implementation 4 Based on Implementation 1, there are also the following implementation methods: like Figures 6 to 10 The static critical surface electrochemical hydrogen peroxide generating device shown comprises a box body 1, wherein the box body 1 comprises an upper box body 7 and a lower box body 8, wherein the upper box body 7 and the lower box body 8 enclose a receiving chamber 11, wherein the upper box body 7 is provided with a box body opening 12 communicating with the receiving chamber 11, a cathode assembly 3 located in the receiving chamber 11 and close to the box body opening 12, and an anode assembly 4 located in the receiving chamber 11 and away from the box body opening 12, wherein the cathode assembly 3 is provided with a phase interface reaction zone 30 communicating with the box body opening 12, wherein the upper side of the phase interface reaction zone 30 forms a gas-solid critical surface with the air of the box body opening 12, and the lower side forms a solid-liquid critical surface with the electrolyte of the receiving chamber 11.

[0128] The present invention sets a phase interface reaction zone 30 on the cathode assembly so that the upper side of the cathode assembly 3 forms a gas-solid critical surface with the air in the box opening 12, thereby increasing the contact area between the cathode and oxygen in the air, so that oxygen can be more fully utilized by the cathode, providing a continuous oxygen supply for the cathode reaction. The lower side of the phase interface reaction zone 30 forms a solid-liquid critical surface with the electrolyte in the accommodating chamber 11, so that the reaction can continue, thereby improving the efficiency and equilibrium concentration of the electrochemical synthesis product and ensuring the continuous preparation of high-concentration products.

[0129] The cathode assembly 3 includes a cathode support 31 close to the box opening 12 and a cathode plate 32 connected to the cathode support 31. The anode assembly 4 includes an anode support 41 away from the box opening 12 and an anode plate 42 connected to the anode support 41. The cathode support 31 is provided with a cathode support opening 310 connected to the box opening 12. The cathode plate 32 is connected to the box opening 12 through the cathode support opening 310. The anode support 41 is provided with an anode support opening 410 connected to the accommodating cavity 11.

[0130] The cathode plate 32 is provided with a hydrophobic gas-permeable layer, and the phase interface reaction zone 30 is located in the hydrophobic gas-permeable layer.

[0131] The upper box body 7 is provided with a supporting portion 71, the supporting portion 71 is provided with a supporting portion opening 72 for the cathode support 31 and the anode support 41 to extend into, a first limiting frame 5 for fixing the cathode support 31, and a second limiting frame 6 for fixing the anode support 41, the cathode support 31 and the anode support 41 are arranged opposite to each other, the first limiting frame 5 and the second limiting frame 6 are arranged in parallel, the cathode sheet 32 ​​and the anode sheet 42 are arranged opposite to each other and in parallel. The second limiting frame 6 is provided with a plurality of limiting grooves 60 for the anode support 41 to extend into, the plurality of limiting grooves 60 are arranged at intervals, and the limiting grooves 60 extend in the horizontal direction.

[0132] The upper box body 7 is provided with a handle 75 and an upper box body positioning portion 70, the lower box body 8 is provided with a lower box body limiting portion 80 matched with the upper box body positioning portion 70, a water inlet 81 and a water outlet 82 respectively connected to the accommodating chamber 11, the accommodating chamber 11 is provided with a drainage portion 111 connected to the water inlet 81, and the drainage portion 111 is provided with a drainage channel connected to the accommodating chamber 11. The water inlet 81 and the water outlet 82 are arranged on both sides of the accommodating chamber 11. The upper box body positioning portion 70 is a protrusion extending toward the accommodating chamber 11, and the lower box body limiting portion 80 is a plane abutting against the lower side of the upper box body 7.

[0133] The cathode support 31 includes a first cathode support 311, a second cathode support 312, and a cathode support accommodating cavity 313 located between the first cathode support 311 and the second cathode support 312, and the cathode sheet 32 ​​is located in the cathode support accommodating cavity 313. The anode support 41 includes a first anode support 411, a second anode support 412, and an anode support accommodating cavity 413 located between the first anode support 411 and the second anode support 412, and the anode sheet 42 is located in the anode support accommodating cavity 413. The cathode support opening 310 is respectively provided in the first cathode support 311 and the second cathode support 312, and the anode support opening 410 is respectively provided in the first anode support 411 and the second anode support 412.

[0134] The first cathode support 311 is provided with a cathode support clamping portion 3111, the second cathode support 312 is provided with a cathode support connecting portion 3121 which cooperates with the cathode support clamping portion 3111, the first anode support 411 is provided with an anode support clamping portion 4111, the second anode support 412 is provided with an anode support connecting portion 4121 which cooperates with the anode support clamping portion 4111, the cathode support 31 is provided with a cathode support connecting groove 33 for one end of the cathode sheet 32 ​​to extend and connect to an external power supply, the anode support 41 is provided with an anode support connecting groove 43 for one end of the anode sheet 42 to extend and connect to an external power supply, the upper box body 7 is provided with a wire groove 74 for the line to pass through, and the wire groove 74 is located on the same side as the cathode support connecting groove 33 and the anode support connecting groove 43.

[0135] The cathode support clamping portion 3111 is a protrusion, the cathode support connecting portion 3121 is a groove, the anode support clamping portion 4111 is a protrusion, and the anode support connecting portion 4121 is a groove.

[0136] The upper box body 7 is provided with a box body positioning portion 13 arranged along the peripheral side of the box body opening 12 and an upper box body opening 73 communicating with the accommodating cavity 11 , and the cathode support 31 is provided with a cathode limiting portion 314 abutting against the box body positioning portion 13 .

[0137] The box positioning portion 13 is a protrusion extending along the peripheral side of the box opening 12 toward the cathode support 31 , and the cathode limiting portion 314 is a side wall of the first cathode support 311 that is attached to the box positioning portion 13 .

[0138] The distance between the anode plate 42 and the cathode plate 32 is 50 mm. The anode plate adopts an iridium-tantalum coated titanium substrate with a coating thickness of 1 μm. The cathode plate adopts titanium material. The cathode catalyst deposited on the surface of the cathode plate is carbon nanotubes.

[0139] Embodiment 5 Embodiment 5 Based on Embodiment 4, the following implementation methods are also provided: A method for preparing hydrogen peroxide by a stationary critical surface electrochemical hydrogen peroxide generator comprises the stationary critical surface electrochemical hydrogen peroxide generator as described above, and the preparation method comprises the following steps: S1, cathode assembly 3 and anode assembly 4 are respectively fixed in the accommodating cavity 11, and the upper side of the cathode assembly 3 is connected to the box opening 12; S2, cathode assembly 3 and anode assembly 4 are electrically connected to an external power supply through wires, electrolyte is added to water tank 1, the upper side of the phase interface reaction zone 30 forms a gas-solid critical surface with the air of the box opening 12, and the electrolyte on the lower side of the phase interface reaction zone 30 forms a solid-liquid critical surface; S3. After power is input, the cathode assembly 3 forms a gas-solid-liquid critical surface, the oxygen generated by the anode assembly 4 reaches the solid-liquid critical surface of the adjacent phase interface reaction zone 30, and the oxygen in the air enters the cathode assembly 3 through the gas-solid critical surface of the adjacent phase interface reaction zone 30 for replenishment, thereby producing hydrogen peroxide.

[0140] The process of hydrogen peroxide generation is as follows: after electricity is input, when a specific volume of electrolyte is added to the reaction water tank, the electrolyte forms a gas-solid-liquid critical surface on the cathode surface. Under the action of the cathode catalyst, a two-electron oxygen reduction reaction takes place on the cathode surface, and the generated hydrogen peroxide will rapidly diffuse in the electrolyte. At this time, the oxygen generated at the anode will reach the cathode critical surface due to buoyancy, and provide supplement to the cathode together with the oxygen in the air. Since the oxygen generated at the anode has a higher purity, the production of hydrogen peroxide can be further increased. When the same amount of hydrogen peroxide is produced, the power consumption of hydrogen peroxide and the required electrolyte concentration can be reduced, which can effectively reduce the use cost of the device.

[0141] In a specific application, the upper and lower critical surface hydrogen peroxide generating device of the present invention can realize intelligent management according to the height of the liquid level in the reaction water storage tank when it is powered on. When the liquid level is away from the cathode critical surface, the generating device automatically disconnects and stops the reaction. In practical applications, the current value of the device can be collected. If the current value is greatly reduced during the operation of the device, it can be judged that there is a lack of water in the reaction water tank. By adding a timer and a water pump, the reaction water can be automatically discharged / replenished.

[0142] In specific applications, the upper and lower critical surface hydrogen peroxide generating device designed in the present invention can be powered by constant voltage and constant current according to actual needs to achieve flexible preparation of hydrogen peroxide and optimize the economy and performance of the reaction device in a suitable voltage and current range.

[0143] In actual application scenarios, when the device is used to prepare hydrogen peroxide, in order to avoid the particles in domestic water or the scale produced by calcium and magnesium ions under the action of the electric field to reduce the reaction effect, it is preferred to use water samples softened by common filters in life and add a small amount of electrolyte to improve the reaction effect.

[0144] Embodiment 6 The difference between Example 6 and Example 4 is that the distance between the anode sheet 42 and the cathode sheet 32 ​​is 20 mm, the anode sheet 42 adopts a metal coating substrate, the cathode sheet 32 ​​adopts a conductive inert metal material, the cathode sheet 32 ​​is provided with a cathode catalyst layer and a hydrophobic breathable resin, and the hydrophobic breathable layer is formed by mixing the cathode catalyst and the hydrophobic breathable resin through secondary sintering. The anode sheet adopts a tin-antimony coated titanium substrate with a coating thickness of 0.7 μm. The cathode sheet adopts nickel material. The cathode catalyst deposited on the surface of the cathode sheet is a nitrogen-doped metal organic framework derived carbon catalyst.

[0145] Method for preparing metal organic framework derived carbon catalyst; N1. Dissolve cobalt nitrate in methanol, stir evenly at room temperature to form a transparent solution, stir at 300 rpm, prepare the cobalt nitrate solution with a concentration of 0.1 mol / L, a molar ratio of cobalt nitrate to 2-methylimidazole of 1:2 to 1:4, react at 80°C, and react for 16 hours to obtain ZIF-67 nanocrystals; N2. The synthesized nanocrystals are pyrolyzed in a nitrogen inert atmosphere with a gas flow rate controlled at 30-100 mL / min, a pyrolysis temperature of 800°C, a heating rate usually controlled at 5°C / min, and a pyrolysis time of 4 hours to obtain a metal organic framework-derived carbon catalyst.

[0146] The hydrophobic and breathable layer is polytetrafluoroethylene resin. The hydrophobic and breathable resin is mixed with the cathode catalyst layer and sintered on the surface of the cathode sheet. The preparation method of the polytetrafluoroethylene resin is as follows: P1, add 700 parts of peroxysuccinic acid, 0.05 parts of perfluorobutylethylene, 5 parts of ammonium perfluoropolyether carboxylate, 50 parts of paraffin, 8 parts of German Wacker HDK H15 hydrophobic silica, 22 parts of carbon nanotubes, and 2 parts of succinic acid to the reaction container in sequence, and stir; P2, introduce nitrogen, control the pressure at 2.7 MPa, temperature at 90°C, add 400 parts of gaseous tetrafluoroethylene monomer, stir at 70 rpm, until the solid content of the emulsion reaches 30%, stop stirring, recover the gaseous monomer, evacuate, and discharge; P3. Collect the obtained polytetrafluoroethylene polymerization liquid, add saturated sodium chloride solution, control the stirring speed to 50 rpm, the polymerization liquid gradually becomes turbid, and the polytetrafluoroethylene particles begin to condense into larger agglomerates. Rinse with deionized water for 5 times, and dry in a 130°C forced air drying oven for about 10 hours. The obtained polytetrafluoroethylene dispersion resin can be packaged and stored.

[0147] On the basis of Example 4, the following implementation method is also provided: the actual performance of the critical surface hydrogen peroxide generator is tested, wherein the power supply voltage of the static upper and lower configuration critical surface hydrogen peroxide generator is 12V, the anode area is the same as the cathode area, and the electrode spacing is 20mm.

[0148] Experimental plan: Add 2L of pure water to a beaker, add 2.84g of sodium sulfate to it to prepare a 0.01M sodium sulfate solution, stir evenly and pour it into the reaction water tank, connect the anode and cathode power supplies in the reaction water tank, and test the hydrogen peroxide concentration in the water tank within 60 minutes.

[0149] Under the condition of 12V direct current, hydrogen peroxide solution was prepared, and samples were taken six times continuously at preset time intervals and tested for 60 minutes to determine the cumulative concentration of hydrogen peroxide in the water.

[0150] like Fig.12 As shown, when using 2L of 0.01M sodium sulfate solution for reaction, the concentration of hydrogen peroxide accumulated in 60min of the critical surface hydrogen peroxide electrochemical generator of the present invention can reach 700ppm. Compared with Example 3, when the hydrogen peroxide production is consistent, the concentration of the required electrolyte is greatly reduced, indicating that the electrochemical generator can realize the preparation of high-concentration hydrogen peroxide solution and reduce the use cost of the device.

[0151] Embodiment 7 Embodiment 7 Based on the above embodiments, the following implementation methods are also provided: the application of the static critical surface electrochemical hydrogen peroxide generator, the prepared hydrogen peroxide is applied to water purification, environmental disinfection, and food processing. The hydrogen peroxide preparation device and method of the present invention can achieve the effective preparation of high-concentration hydrogen peroxide, has a wide range of application prospects and significant cost advantages, and when the high-concentration hydrogen peroxide product is used for environmental sterilization, removal of organic pollutants, water purification, etc., a significant effect can be achieved.

[0152] On the basis of Example 3 and Example 6, the present invention can quickly obtain high-concentration hydrogen peroxide through a static critical surface hydrogen peroxide module generator. Compared with traditional methods, the upper limit of electrochemical hydrogen peroxide concentration can be greatly improved, and the product concentration can reach more than 1000 mg / L.

[0153] The present invention constructs an electrochemical interface by adjusting materials and structures, forms a gas-solid-liquid equilibrium interface on the cathode catalyst surface, and improves the electrochemical reaction efficiency. Compared with the existing electrochemical preparation method, the hydrogen peroxide generation efficiency is increased by more than 80%, the selectivity of the two-electron oxygen reduction reaction reaches more than 90%, the occurrence of side reactions is reduced, and the product quality is improved.

[0154] The diversified preparation method parameter regulation and combination innovation of the present invention can meet a wider range of user needs, and the concentration, purity and other parameters of hydrogen peroxide can be customized according to specific application scenarios, thereby expanding the application scope of the present invention.

[0155] The interface electrochemical device of the present invention adopts a diaphragm-free integrated design, with the positive and negative electrodes placed in the same electrolyte chamber. The internal structure is simple and compact, which is conducive to integration and modularization, and can achieve rapid configuration and power regulation in different application scenarios.

[0156] The surfaces of the anode and cathode of the present invention are respectively loaded with a high-efficiency ORR catalyst and an OER catalyst, which optimizes the electrode reaction kinetics, greatly increases the generation rates of hydrogen peroxide and ozone, and reduces energy consumption.

[0157] Compared with the traditional preparation process, the present invention has obvious advantages in equipment investment, energy consumption, operation and maintenance, product application, etc., and can significantly improve economic and social benefits.

[0158] The above examples are only used to further illustrate the technical content of the present invention, so that readers can understand it more easily, but they do not mean that the implementation of the present invention is limited to this. Any technical extension or re-creation made according to the present invention is protected by the present invention. The protection scope of the present invention shall be subject to the claims.

Claims

1. A stationary critical surface electrochemical hydrogen peroxide generating device, comprising a housing (1), wherein the housing (1) is provided with a containing cavity (11), and characterized in that: One side of the box body (1) is provided with a box body opening (12) connected to the accommodating chamber (11), a cathode assembly (3) located in the accommodating chamber (11) and close to the box body opening (12), and an anode assembly (4) located in the accommodating chamber (11) and away from the box body opening (12); the cathode assembly (3) is provided with a hydrophobic air-permeable layer; the hydrophobic air-permeable layer is provided with a phase interface reaction zone (30) connected to the box body opening (12); one side of the phase interface reaction zone (30) forms a gas-solid critical surface with the air of the box body opening (12), and the other side forms a solid-liquid critical surface with the electrolyte in the accommodating chamber (11).

2. The static critical surface electrochemical hydrogen peroxide generator according to claim 1, characterized in that: The cathode assembly (3) comprises a cathode support (31) close to the box opening (12) and a cathode plate (32) connected to the cathode support (31); the anode assembly (4) comprises an anode support (41) away from the box opening (12) and an anode plate (42) connected to the anode support (41); the cathode support (31) is provided with a cathode support opening (310) communicating with the box opening (12); the cathode plate (32) is communicated with the box opening (12) through the cathode support opening (310); the anode support (41) is provided with an anode support opening (410) communicating with the accommodating cavity (11); and the hydrophobic air-permeable layer is located on the cathode plate (32).

3. The static critical surface electrochemical hydrogen peroxide generator according to claim 2, characterized in that: The distance between the anode sheet (42) and the cathode sheet (32) is between 2 and 50 mm. The anode sheet (42) uses a metal coating substrate, the cathode sheet (32) uses a conductive inert metal material, and the hydrophobic and breathable layer includes a cathode catalyst layer and a hydrophobic and breathable resin.

4. The static critical surface electrochemical hydrogen peroxide generator according to claim 3 is characterized in that: The anode plate is made of one of platinum-plated, iridium-tantalum or tin-antimony coated titanium substrates, with a coating thickness of 0.1μm-1μm, and the cathode plate is made of one of aluminum, titanium, stainless steel, nickel, and platinum-titanium.

5. The static critical surface electrochemical hydrogen peroxide generator according to claim 3, characterized in that: The cathode catalyst layer adopts a nano-carbon-based catalyst, and the hydrophobic and breathable layer is made by mixing the cathode catalyst layer and a hydrophobic and breathable resin.

6. The static critical surface electrochemical hydrogen peroxide generator according to claim 3, characterized in that: The box body (1) is provided with a first limiting frame (5) for fixing the cathode support (31), and a second limiting frame (6) for fixing the anode support (41); the cathode support (31) and the anode support (41) are arranged opposite to each other, the cathode sheet (32) and the anode sheet (42) are arranged opposite to each other, and the second limiting frame (6) is provided with a plurality of limiting grooves (60) for the anode support (41) to extend into, and the plurality of limiting grooves (60) are arranged at intervals.

7. The static critical surface electrochemical hydrogen peroxide generator according to claim 6, characterized in that: The cathode support (31) comprises a first cathode support (311), a second cathode support (312), and a cathode support accommodating cavity (313) located between the first cathode support (311) and the second cathode support (312); the cathode sheet (32) is located in the cathode support accommodating cavity (313); the anode support (41) comprises a first anode support (411), a second anode support (412), and an anode support accommodating cavity (413) located between the first anode support (411) and the second anode support (412); the anode sheet (42) is located in the anode support accommodating cavity (413); the cathode support opening (310) is respectively provided in the first cathode support (311) and the second cathode support (312); and the anode support opening (410) is respectively provided in the first anode support (411) and the second anode support (412).

8. The static critical surface electrochemical hydrogen peroxide generator according to claim 7, characterized in that: The first cathode support (311) is provided with a cathode support clamping portion (3111), the second cathode support (312) is provided with a cathode support connecting portion (3121) that cooperates with and is connected to the cathode support clamping portion (3111), the first anode support (411) is provided with an anode support clamping portion (4111), the second anode support (412) is provided with an anode support connecting portion (4121) that cooperates with and is connected to the anode support clamping portion (4111), the cathode support (31) is provided with a cathode support connecting groove (33) through which one end of the cathode sheet (32) extends to be connected to an external power source, and the anode support (41) is provided with an anode support connecting groove (43) through which one end of the anode sheet (42) extends to be connected to an external power source.

9. A method for preparing hydrogen peroxide using a static critical surface electrochemical hydrogen peroxide generator, characterized in that: The static critical surface electrochemical hydrogen peroxide generator according to any one of claims 1 to 9 is prepared by the following steps: S1, the cathode assembly (3) and the anode assembly (4) are respectively fixed in the accommodating cavity (11), and one side of the cathode assembly (3) is connected to the box opening (12); S2, the cathode assembly (3) and the anode assembly (4) are electrically connected to an external power supply through wires, and an electrolyte is added to the water tank (1). One side of the phase interface reaction zone (30) forms a gas-solid critical surface with the air in the box opening (12), and the electrolyte forms a solid-liquid critical surface on the other side of the phase interface reaction zone (30); S3. After the power is input, the cathode assembly (3) forms a gas-solid-liquid critical surface, the oxygen generated by the anode assembly (4) reaches the solid-liquid critical surface of the phase interface reaction zone (30), and the oxygen in the air enters the cathode assembly (3) through the gas-solid critical surface of the phase interface reaction zone (30) for replenishment, thereby producing hydrogen peroxide.

10. Application of a stationary critical surface electrochemical hydrogen peroxide generator, characterized in that: The prepared hydrogen peroxide is used in water purification, environmental disinfection and food processing.

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