An electrochemical in-situ generating device for reactive oxygen species and its control method

Abstract

This invention relates to the field of electrochemical technology, specifically to an electrochemical in-situ active oxygen generator and its control method. The device includes a housing and a reaction chamber. The housing comprises a first housing and a second housing enclosing the reaction chamber, an anode assembly and a cathode assembly located within the reaction chamber, and the second housing has an opening. The second housing completely surrounds the anode and cathode assemblies, and its projection is arc-shaped. This invention achieves physical protection and impurity interception of the electrode assembly while effectively eliminating short-circuit flow through fluid dynamics guidance, extending the equivalent residence time of the reaction liquid on the electrode surface, and improving the efficiency of active oxygen generation and the lifespan of the device. With dual-mode power switching, this invention can first generate a first active oxygen species using DC power, and then switch to pulse power to convert it into a second active oxygen species with a higher oxidation potential, thereby improving oxidation efficiency while ensuring electrode stability.

Description

Technical Field

[0001] This invention relates to the field of electrochemical technology, specifically to an electrochemical in-situ generating device for producing reactive oxygen species and its control method. Background Technology

[0002] Reactive oxygen species (ROS) exhibit broad application prospects in water treatment, sterilization, and textile cleaning due to their strong oxidizing properties, rapid reaction rates, and environmentally friendly reaction products. Electrochemical methods, with their advantages of in-situ generation, controllable process, and no need for external chemical oxidants, have become one of the mainstream technologies for ROS preparation.

[0003] For example, Chinese patent document CN121737963A discloses an electrochemical hydrogen peroxide generator and a washing machine integrated into the drum of a washing machine. This device uses a first and second shell assembled to form a reaction space, internally integrating a cathode assembly and an anode assembly. However, under actual washing conditions, this structure has the following limitations: First, while the second shell has a large opening on its side for fluid exchange, forming a semi-enclosed design for the electrodes, the lack of an effective flow guiding and interception structure allows fibers, hair, lint, and solid particles in the washing water to easily enter the reaction zone directly with the water flow, entangle or deposit on the electrode surface, resulting in the covering of electrode active sites and a decrease in the effective reaction area. Second, when the washing machine drum rotates at high speed, the water flow is in a strongly turbulent state. The existing opening layout of the second shell easily causes the water flow to form a "short-circuit flow," resulting in insufficient residence time of the reaction liquid on the electrode surface. Dissolved oxygen and other reactants are quickly carried away from the reaction chamber before sufficient mass transfer and conversion, which to some extent limits the current efficiency of the electrochemical reaction and the steady-state yield of the active substances, leading to a low overall preparation efficiency.

[0004] To address the aforementioned shortcomings, it is necessary to optimize and improve the structure of existing generating devices to enhance the efficiency of reactive oxygen species production and the operational reliability of the devices. Summary of the Invention

[0005] Regarding the aforementioned technical problems in existing generating devices, where foreign matter becomes entangled or deposited on the electrode surface, resulting in the covering of electrode active sites, reduction of effective reaction area, and insufficient residence time of the reaction solution on the electrode surface, the technical solution adopted by the present invention to solve these problems is as follows: An electrochemical in-situ generating device for reactive oxygen species includes a housing and a reaction chamber located within the housing. The housing includes a first housing and a second housing that enclose the reaction chamber, an anode assembly and a cathode assembly located within the reaction chamber. The second housing has multiple openings for liquid to pass through. The second housing continuously surrounds the anode assembly and the cathode assembly, and the projection of the second housing is arc-shaped. The cathode assembly is connected to a DC power supply assembly, and the anode assembly is connected to a dual-mode power supply. When the anode assembly is connected to the dual-mode power supply in DC power supply mode, the anode assembly and the cathode assembly jointly generate a first reactive oxygen species. When the anode assembly is connected to the dual-mode power supply in pulse power supply mode, the anode assembly and the cathode assembly jointly convert the first reactive oxygen species or its intermediates already generated in the liquid into a second reactive oxygen species with a higher redox potential.

[0006] Furthermore, in some embodiments of the present invention, the second housing is columnar, and the opening is circular, elliptical, or polygonal. The second housing is ultrasonically welded to the first housing.

[0007] Furthermore, in some embodiments of the present invention, the second housing is provided with a second housing opening, the opening including a side opening located on the side of the second housing and a bottom opening located at the bottom of the second housing, and both the side opening and the bottom opening are provided in multiples.

[0008] Furthermore, in some embodiments of the present invention, the first housing is provided with an extension extending toward the second housing. The extension is provided with a first peripheral limiting extension on its periphery and a second inner extension on its inner side. The first peripheral limiting extension is provided with a first limiting groove for limiting the anode assembly and a second limiting groove for limiting the cathode assembly. The second inner extension is provided with a third limiting groove for limiting the anode assembly and a fourth limiting groove for limiting the cathode assembly. The first limiting groove and the third limiting groove are located on the same straight line, and the second limiting groove and the fourth limiting groove are located on the same straight line. The bottom of the second housing is provided with a fifth limiting groove for limiting the anode assembly and a sixth limiting groove for limiting the cathode assembly.

[0009] Furthermore, in some embodiments of the present invention, the first peripheral limiting extension includes a first extending end, a second extending end, and a third extending end located between the first extending end and the second extending end; the first limiting groove is located between the first extending end and the third extending end; the second limiting groove is located between the second extending end and the third extending end; the second inner extension includes a fourth extending end, a fifth extending end, and a sixth extending end located between the fourth extending end and the fifth extending end; the third limiting groove is located between the fourth extending end and the sixth extending end; and the fourth limiting groove is located between the fifth extending end and the sixth extending end.

[0010] Furthermore, in some embodiments of the present invention, the extension portion is provided with a plurality of third limiting extension portions located on its periphery, a first extension end connecting groove is provided between the third limiting extension portion and the first periphery limiting extension portion, a second extension end connecting groove is provided between two adjacent third limiting extension portions, the second housing is provided with a first positioning extension portion extending into the first extension end connecting groove, a second positioning extension portion extending into the second extension end connecting groove, a first positioning connecting groove into which the first periphery limiting extension portion extends, and a second positioning connecting groove into which the third limiting extension portion extends.

[0011] Furthermore, in some embodiments of the present invention, the distance between the anode assembly and the cathode assembly is 1-3 mm, the reaction chamber includes a reaction space located between the anode assembly and the cathode assembly, the side opening includes a reaction space side opening communicating with the side of the reaction space, the reaction space side opening is provided in two sets and is arranged opposite to each other on both sides of the reaction space, and the bottom opening includes a reaction space bottom opening communicating with the bottom of the reaction space.

[0012] Furthermore, in some embodiments of the present invention, the anode assembly is a titanium-based catalytic electrode, the cathode assembly is a gas diffusion electrode, the cathode assembly is provided with a water-permeable hole, the first housing is provided with a first slot for the conductive part of the anode assembly to extend out and a second slot for the conductive part of the cathode assembly to extend out, the first slot is located between the first limiting slot and the third limiting slot, the second slot is located between the second limiting slot and the fourth limiting slot, and the first slot and the second slot are offset relative to each other.

[0013] Furthermore, in some embodiments of the present invention, the cathode assembly is provided with a water-permeable hole, the anode assembly and the cathode assembly extend along the central axis of the second housing, the reaction chamber includes an anode assembly space located between the inner walls of the anode assembly and the second housing, and a cathode assembly space located between the inner walls of the cathode assembly and the second housing, the reaction space is located between the anode assembly space and the cathode assembly space, the side opening includes an anode assembly space side opening communicating with the side of the anode assembly space and a cathode assembly space side opening communicating with the side of the cathode assembly space, and the bottom opening includes an anode assembly space bottom opening communicating with the bottom surface of the anode assembly space and a cathode assembly space bottom opening communicating with the bottom surface of the cathode assembly space.

[0014] Another objective of the invention is to provide a control method for an electrochemical in-situ reactive oxygen species generator, comprising the electrochemical in-situ reactive oxygen species generator as described above, wherein the control method comprises the following steps: S1. The cathode assembly is connected to the DC power supply assembly, and the anode assembly is connected to the dual-mode power supply. S2. When the cathode component is connected to the DC voltage of the DC power supply component and the anode component is connected to the DC voltage of the dual-mode power supply, the cathode component and the anode component cooperate to undergo an electrochemical reaction to generate a first active oxygen species. S3. When the cathode component is connected to the DC voltage of the DC power supply component and the anode component is connected to the pulse voltage of the dual-mode power supply, the anode component uses the transient high potential generated by the pulse voltage to further convert the first active oxygen species or its intermediate in the liquid into a second active oxygen species with a higher redox potential.

[0015] The beneficial effects of this invention are as follows: 1. This invention, through the continuous surrounding arc-shaped structure and porous arrangement of the second shell, achieves physical protection and impurity interception of the electrode assembly while effectively eliminating short-circuit flow by utilizing fluid dynamics guidance. This extends the equivalent residence time of the reaction liquid on the electrode surface, improving the efficiency of active oxygen preparation and the lifespan of the device. Combined with dual-mode power switching, this invention can first generate the first active oxygen species using DC power, and then switch to pulse power to convert it into a second active oxygen species with a higher oxidation potential, thereby improving oxidation efficiency while ensuring electrode stability.

[0016] 2. The control method of the present invention ensures the basic oxygen reduction reaction by using cathode DC power supply and switches between anode DC / pulse dual modes to regulate the reaction path, thereby achieving the steady-state generation of the first active oxygen species and the directional conversion to the second active oxygen species with a high oxidation potential. While adapting to different water qualities and washing conditions, it improves the gradient yield and oxidation capacity of active oxygen, and balances the sterilization and purification efficiency with the operating energy consumption. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of an electrochemical in-situ active oxygen generation device according to the present invention.

[0018] Figure 2 This is a top view of an electrochemical in-situ active oxygen generator according to the present invention.

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

[0020] Figure 4 for Figure 2 BB cross-sectional view.

[0021] Figure 5 This is an exploded view of an electrochemical in-situ active oxygen generator according to the present invention.

[0022] Figure 6 This is an exploded view from another angle of an electrochemical in-situ active oxygen generation device according to the present invention.

[0023] Figure 7 This is a schematic diagram of the first housing of the present invention.

[0024] Figure 8 This is a schematic diagram showing the connection of the second housing of the present invention to the anode assembly and the cathode assembly, respectively.

[0025] Explanation of reference numerals in the attached figures: 1. Shell, 2. Reaction chamber, 3. First shell, 4. Second shell, 5. Anode assembly, 6. Cathode assembly, 7. Extension, 8. Reaction space, 9. Sealing ring, 31. First slot, 32. Second slot, 41. Opening, 411. Side opening, 412. Bottom opening, 42. Second shell opening, 44. First positioning extension, 45. Second positioning extension, 46. First positioning connecting groove, 47. Second positioning connecting groove, 48. Fifth limiting groove, 49. Sixth limiting groove, 50. Anode assembly space, 501. Side opening of anode assembly space, 502. Bottom opening of anode assembly space, 60. Cathode assembly space. 601. Side opening of cathode assembly space; 602. Bottom opening of cathode assembly space; 61. Water permeable hole; 71. First peripheral limiting extension; 72. Second inner extension; 73. Third limiting extension; 74. First extension end connecting groove; 75. Second extension end connecting groove; 701. First limiting groove; 702. Second limiting groove; 703. Third limiting groove; 704. Fourth limiting groove; 711. First extension end; 712. Second extension end; 713. Third extension end; 721. Fourth extension end; 722. Fifth extension end; 723. Sixth extension end; 81. Side opening of reaction space; 82. Bottom opening of reaction space. Detailed Implementation

[0026] The embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0027] like Figure 1 , Figure 3 , Figure 4 and Figure 5 An electrochemical in-situ reactive oxygen species generating device is shown, comprising a housing 1 and a reaction chamber 2 located within the housing 1. The housing 1 includes a first housing 3 and a second housing 4 enclosing the reaction chamber 2, an anode assembly 5 and a cathode assembly 6 located within the reaction chamber 2. The second housing 4 has multiple openings 41 for liquid to pass through. The second housing 4 is continuously arranged around the outside of the anode assembly 5 and the cathode assembly 6, and the projection of the second housing 4 is arc-shaped. The cathode assembly 6 is connected to a DC power supply assembly, and the anode assembly 5 is connected to a dual-mode power supply, which has DC power supply and pulse power supply modes. When the anode assembly 5 is switched to the dual-mode power supply in DC power supply mode, the anode assembly 5 and the cathode assembly 6 synergistically generate a first reactive oxygen species. When the anode assembly 5 is switched to the dual-mode power supply in pulse power supply mode, the anode assembly 5 and the cathode assembly 6 synergistically convert the first reactive oxygen species or its intermediates already generated in the liquid into a second reactive oxygen species with a higher redox potential.

[0028] This invention, through a continuous enclosing arc-shaped structure in conjunction with the first shell and the porous design of the second shell, achieves physical protection and impurity interception of the electrode assembly. Simultaneously, it utilizes fluid dynamics to effectively eliminate short-circuit flow, extending the equivalent residence time of the reaction solution on the electrode surface, thereby improving the efficiency of active oxygen preparation and the lifespan of the device. Furthermore, this invention, combined with dual-mode power switching, allows for the initial generation of a first active oxygen species using DC power, followed by switching to pulse power to convert it into a second active oxygen species with a higher oxidation potential, thus improving oxidation efficiency while ensuring electrode stability.

[0029] The second shell continuously surrounds the anode and cathode components, forming a complete physical barrier between the electrode components and the external turbulent environment and impurities, compared to a semi-enclosed structure. Multiple openings maintain normal liquid exchange while utilizing the shell boundary to achieve primary interception of fibers, hair, and large solid particles in the washing water, preventing impurities from directly entering the reaction chamber and depositing on the electrode surface. This reduces the coverage of electrode active sites and the attenuation of the effective reaction area, thus extending the device's maintenance cycle and service life.

[0030] Furthermore, the cross-sectional projection of the second shell is arc-shaped, a shape that adapts to the fluid dynamics characteristics of applications such as washing machine drums. The arc-shaped surface guides the flow of liquid, avoiding local dead zones formed by sharp edges. Combined with the continuous enclosing structure, the liquid entering the reaction chamber is throttled and guided by the openings and the chamber itself, altering the original "short-circuit flow" path, reducing the penetration velocity at the electrode surface, increasing the equivalent residence time of the reaction liquid on the electrode surface, and promoting more complete mass transfer and electrochemical conversion of reactants such as dissolved oxygen at the electrode interface.

[0031] like Figure 1 , Figure 5 , Figure 6 and Figure 8 The device shown is an electrochemical in-situ generating device for active oxygen, wherein the second housing 4 is columnar, and the opening 41 is circular, elliptical, or polygonal. The second housing 4 is non-detachably connected to the first housing 3.

[0032] Specifically, the columnar structure can provide internal reaction space while withstanding the fluid pressure in the washing environment, and the perforated openings can throttle and equalize the flow of water entering the reaction chamber, allowing the liquid to pass through the electrode surface in a relatively stable state, avoiding excessive flow rate due to large openings, thereby prolonging the effective contact time of the reaction liquid on the electrode surface.

[0033] Optionally, the opening 41 can be a circular hole, an elliptical hole, a long strip hole, or a hexagonal hole.

[0034] The fixed connection between the second housing and the first housing helps to enhance the overall sealing and structural integrity of the device, reduce the relative positional shift of the internal electrode components under long-term vibration conditions, and thus help maintain the uniformity of the electric field distribution and the continuous stability of the electrochemical reaction.

[0035] Because washing machines frequently come into contact with disinfectants, laundry detergents, and other cleaning agents, the active substances generated by the generator are corrosive. Screws or clips with detachable structures can corrode or lose strength in long-term humid environments. Rusty screws can easily contaminate the cleaning solution with rust, and clips can easily loosen during prolonged high-speed rotation, affecting the stability of the generator. Optionally, in some embodiments, the second housing and the first housing can be fixedly connected by ultrasonic welding, hot plate welding, laser welding, adhesive bonding, riveting, etc. Non-detachable connections offer good sealing and strong vibration resistance, making them suitable for applications requiring long-term reliable sealing.

[0036] like Figure 1 , Figure 3 and Figure 5 The device shown is an electrochemical in-situ generating device for active oxygen. The second housing 4 is provided with a second housing opening 42. The opening 41 includes a side opening 411 located on the side of the second housing 4 and a bottom opening 412 located at the bottom of the second housing 4. Both the side opening 411 and the bottom opening 412 are provided in multiples.

[0037] Specifically, by setting multiple openings on the sides and bottom of the second shell, multi-directional fluid channels can be formed inside the reaction chamber, reducing local flow dead zones that may be caused by water entering from one direction, and helping to improve the uniformity of the reaction liquid distribution on the electrode surface. The distributed opening structure maintains the total fluid exchange area while the individual pore diameter is relatively small, which can play a certain role in screening and blocking external impurities.

[0038] During installation, the opening of the second housing can be oriented towards the first housing to enclose the anode and cathode components. The side openings and bottom openings work together to ensure that the device can maintain a stable flow capacity under different water level conditions, which is beneficial to maintaining the stability of active oxygen production efficiency in complex and dynamic washing environments.

[0039] like Figure 1 , Figure 6 and Figure 7The device shown is an electrochemical in-situ generating device for active oxygen. The first housing 3 has an extension 7 extending toward the second housing 4. The extension 7 has a first peripheral limiting extension 71 on its periphery and a second inner extension 72 on its inner side. The first peripheral limiting extension 71 has a first limiting groove 701 that limits the anode assembly 5 and a second limiting groove 702 that limits the cathode assembly 6. The second inner extension 72 has a third limiting groove 703 that limits the anode assembly 5 and a fourth limiting groove 704 that limits the cathode assembly 6. The first limiting groove 701 and the third limiting groove 703 are located on the same straight line, and the second limiting groove 702 and the fourth limiting groove 704 are located on the same straight line.

[0040] Specifically, by providing an extension in the first housing, the first peripheral limiting extension and the second inner extension can form multi-point support and double-sided limiting for the anode and cathode assemblies within the reaction chamber. This enhances the structural rigidity of the electrode assemblies within the housing, prevents current instability caused by fluctuations in the inter-electrode distance, and ensures the stability of active oxygen production. The collinear layout of the first to fourth limiting grooves ensures the axial alignment of the anode and cathode assemblies after assembly, maintains the consistency of the inter-electrode distance, and effectively prevents the electrodes from deflecting or displacing under fluid impact, thereby ensuring the uniformity of the electric field distribution within the reaction chamber. Simultaneously, the corresponding relationship of the limiting grooves helps simplify positioning operations during assembly and improves the consistency of component installation.

[0041] like Figure 1 , Figure 6 and Figure 7 The device shown is for generating reactive oxygen species in situ using electrochemical methods. The first peripheral limiting extension 71 includes a first extension end 711, a second extension end 712, and a third extension end 713 located between the first extension end 711 and the second extension end 712. A first limiting groove 701 is located between the first extension end 711 and the third extension end 713. A second limiting groove 702 is located between the second extension end 712 and the third extension end 713. The second inner extension 72 includes a fourth extension end 721, a fifth extension end 722, and a sixth extension end 723 located between the fourth extension end 721 and the fifth extension end 722. The third limiting groove 703 is located between the fourth extension end 721 and the sixth extension end 723. The fourth limiting groove 704 is located between the fifth extension end 722 and the sixth extension end 723.

[0042] Specifically, this invention constructs a comb-like positioning structure by providing specific extension ends to the first peripheral limiting extension and the second inner extension, and forming limiting grooves between adjacent extension ends, thereby achieving multi-point synchronous constraint of the anode and cathode assemblies. This segmented extension end design enhances the bending strength of the limiting structure, ensuring that the electrode assembly maintains a constant electrode spacing even when subjected to vibration or water flow impact. Simultaneously, the physical isolation between the third and sixth extension ends effectively avoids the risk of short circuits caused by contact between the anode and cathode. Furthermore, the combination of multiple extension ends and multiple limiting grooves simplifies positioning operations during assembly, improves the consistency of electrode installation, and enhances the long-term reliability of the device.

[0043] like Figure 4 , Figure 6 , Figure 7 and Figure 8 The device shown is an electrochemical in-situ active oxygen generator. The extension 7 is provided with a plurality of third limiting extensions 73 located on its periphery. A first extension end connecting groove 74 is provided between the third limiting extension 73 and the first periphery limiting extension 71. A second extension end connecting groove 75 is provided between two adjacent third limiting extensions 73. The second housing 4 is provided with a first positioning extension 44 extending into the first extension end connecting groove 74, a second positioning extension 45 extending into the second extension end connecting groove 75, a first positioning connecting groove 46 into which the first periphery limiting extension 71 extends, and a second positioning connecting groove 47 into which the third limiting extension 73 extends.

[0044] Specifically, the extension section is provided with multiple third limiting extension sections, forming a first extension end connecting groove between the extension section and the first circumferential limiting extension section, and a second extension end connecting groove between adjacent third limiting extension sections. The second housing is correspondingly provided with extension sections extending into the aforementioned grooves and connecting grooves for the extension sections to enter. This allows the first and second housings to achieve circumferential positioning and axial limiting through the interlocking of multiple sets of concave and convex structures during assembly, which helps improve the docking accuracy of housing assembly and the consistency of repeated assembly. The cooperation between the grooves and the extension sections forms an interlocking interface after the housing is closed, which can disperse the shear stress generated by water flow pulsation or drum rotation, suppress the relative displacement between housings, and help maintain the sealing integrity of the reaction chamber and the positioning stability of the internal electrode components. At the same time, this interlocking method can provide positioning guidance during assembly, reducing the possibility of installation misalignment.

[0045] like Figure 1 , Figure 3 , Figure 4 and Figure 5The device shown is an electrochemical in-situ generating device for active oxygen, wherein the outer side of the extension 7 is flush with the outer side of the second housing 4, the diameter of the extension 7 is equal to the diameter of the second housing 4, and the second housing 4 is ultrasonically welded to the first housing 3.

[0046] In this embodiment, the outer side of the extension is flush with the outer side of the second housing, and both have equal diameters and widths. This ensures that the outer surfaces of the first and second housings remain flat and continuous after assembly, which helps reduce local turbulence and the accumulation of fibrous impurities at the connection point. The second housing is fixed to the first housing by ultrasonic welding, forming a fusion at the connection interface. Compared to mechanical connections, this provides better sealing strength and fatigue resistance, reducing the risk of leakage or cracking of the housing under long-term vibration and alternating water pressure. Furthermore, the flush welding end faces facilitate the uniform transmission of ultrasonic energy, improving the consistency of welding quality and thus enhancing the overall structural reliability of the device.

[0047] like Figure 3 , Figure 4 , Figure 6 and Figure 8 The device shown is an electrochemical in-situ generating device for active oxygen. The bottom of the second housing 4 is provided with a fifth limiting groove 48 for limiting the anode assembly 5 and a sixth limiting groove 49 for limiting the cathode assembly 6. The distance between the anode assembly 5 and the cathode assembly 6 is 1-3 mm. The reaction chamber 2 includes a reaction space 8 located between the anode assembly 5 and the cathode assembly 6. The reaction space 8 is connected to the side opening 411 and the bottom opening 412 respectively. The side opening 411 is provided in two sets and is arranged opposite to each other on both sides of the reaction space 8. The bottom opening 412 is provided in multiple sets and is connected to the bottom of the reaction space 8.

[0048] Specifically, the bottom of the second housing is provided with a fifth limiting groove for limiting the anode assembly and a sixth limiting groove for limiting the cathode assembly. Together with the limiting structure in the first housing, it can form a fixed support for the electrode assembly at both the upper and lower ends, reduce the swaying of the electrode plates caused by water flow impact, and help maintain a constant electrode spacing.

[0049] Specifically, the side opening 411 includes a reaction space side opening 81 that communicates with the side of the reaction space 8, and the reaction space side opening 81 is provided in two sets and is arranged opposite to each other on both sides of the reaction space 8. The bottom opening 412 includes a reaction space bottom opening 82 that communicates with the bottom of the reaction space 8.

[0050] In this embodiment, the reaction space is directly connected to the side openings of the reaction space arranged opposite to each other on both sides and to multiple bottom openings of the reaction space evenly distributed at the bottom. The oppositely arranged side openings allow liquid to be symmetrically discharged from both sides of the reaction space under the dynamic pressure of the rotating drum, reducing the flow dead zone that may be generated by unidirectional water inflow and facilitating uniform contact between the electrode surface and the reactants. The side openings of the reaction space maintain the continuity of fluid discharge from the bottom of the reaction space under different water levels and rotation angles. By directly aligning the side openings and bottom openings of the reaction space with the narrow 1-3mm slit between the anode and cathode, a throttling effect is created by utilizing spatial physical constraints, extending the residence time of the reaction liquid on the electrode surface, thereby reducing electrolysis energy consumption while maintaining mass transfer efficiency and improving the stability of reactive oxygen generation. Figure 2 , Figure 3 , Figure 4 and Figure 7 The device shown is an electrochemical in-situ generating device for reactive oxygen species. The anode assembly 5 is a titanium-based catalytic electrode, and the cathode assembly 6 is a gas diffusion electrode. The first housing 3 is provided with a first slot 31 for the conductive part of the anode assembly 5 to extend out and a second slot 32 for the conductive part of the cathode assembly 6 to extend out. The first slot 31 is located between the first limiting slot 701 and the third limiting slot 703, and the second slot 32 is located between the second limiting slot 702 and the fourth limiting slot 704. The first slot 31 and the second slot 32 are offset from each other.

[0051] Specifically, the staggered relative arrangement of the first and second slots can increase the external creepage distance between the positive and negative conductive parts, reduce the possibility of electrical short circuits caused by humid environments, and thus improve the operational reliability of the device under high humidity conditions.

[0052] like Figure 2 The illustrated device for in-situ electrochemical generation of active oxygen includes a first housing with cathode and anode markings. The cathode assembly is electrically connected to the negative electrode connector, and the anode assembly is electrically connected to the positive electrode connector, enabling external power supply. The lead outlets of the negative and positive electrode connectors are double-encapsulated with PTFE insulating sleeves and epoxy resin, ensuring electrical safety and improving the corrosion resistance of the electrode leads, thus ensuring stable operation of the device in complex media environments. Optionally, in some embodiments, a sealing ring 9 can be provided on the first housing. The sealing ring can be used to seal the connection between the generating device and connecting components such as the bottom of a washing machine drum. Of course, in some embodiments, the size of the sealing ring 9 can be adjusted so that it is sealed on the outside of the connection between the first and second housings. The sealing ring 9 can achieve long-term reliable sealing within a temperature range of -20℃ to 200℃, preventing leakage from the reaction chamber and ensuring the airtightness of the reaction system.

[0053] In this embodiment, the combination of the anode and cathode components helps reduce reaction energy consumption and improve electrocatalytic efficiency. The anode component uses a titanium-based catalytic electrode, and the cathode component uses a gas diffusion electrode. The titanium-based catalytic electrode has good corrosion resistance, which helps extend the electrode's service life in washing environments. The porous structure of the gas diffusion electrode increases the gas-liquid-solid three-phase reaction interface, promotes the mass transfer of dissolved oxygen to the electrode surface, and reduces the occurrence of hydrogen evolution side reactions, thereby maintaining the selective generation of active oxygen at lower current densities.

[0054] Specifically, the substrate of the anode assembly is a pure titanium plate with a thickness of 0.1-0.3 mm; its coating includes a TiO2-based modified coating or a tin-antimony-based modified coating.

[0055] The TiO2-based modified coating was prepared using the sol-gel method to create a La-doped TiO2 composite coating. The La doping amount was 0.5%-2.0% (molar ratio), the coating thickness was 1.0-3.0 μm, the sintering temperature was 500-550℃, and the holding time was 2-3 h. The specific preparation steps of the anode component with the TiO2-based modified coating are as follows: M1. Titanium-based pretreatment: Take a pure titanium plate with a thickness of 0.1-0.3 mm, remove the surface oxide film by mechanical grinding, immerse it in a 10-15 wt% NaOH solution, and keep it at 60-80℃ for 30-60 min to remove organic stains; then transfer it to a mixed acid solution with a volume ratio of HF:HNO3:H2O of 1:2:10, and etch it at room temperature for 1-3 min to form a micron-level roughness; ultrasonically clean it with deionized water for 10 min, and dry it at 80℃ for later use. M2. Sol preparation: Tetrabutyl titanate was used as the titanium source and lanthanum nitrate hexahydrate was used as the lanthanum source. The lanthanum source was dissolved in anhydrous ethanol at a molar ratio of La / (La+Ti) of 0.5%-2.0%. Acetylacetone was added as a complexing agent. After stirring, deionized water was added dropwise for hydrolysis. After aging for 24 hours, La-doped TiO2 sol was obtained. The amount of acetylacetone added was 0.5-1.0 times the molar amount of titanium source, and the amount of deionized water added was 1-2 times the molar amount of titanium source. A transparent, precipitate-free La-doped TiO2 sol was obtained, with the solid concentration controlled at 0.6-0.9 mol / L.

[0056] M3. Coating and Drying: Immerse the pretreated titanium base in the sol and pull it up at a uniform speed of 1-3 mm / s, with an ambient humidity of 30%-45%. After pulling, dry at 80-100℃ for 5-10 minutes to allow the solvent to evaporate, the gel network to be initially solidified, and a single-layer gel film to be formed. M4, Multi-layer accumulation: Repeat step M3 for 3-10 coating-drying cycles. After each 2-3 coating cycles, perform intermediate heat treatment at 300-350℃ for 10-15 minutes to decompose residual organic matter and release internal stress, preventing cracking or peeling during final sintering. Accumulate the coating thickness to 1.0-3.0μm. M5. Final sintering: The coated electrode is placed on a ceramic carrier plate and heated to 500-550℃ at a rate of 2-5℃ / min. The temperature is maintained for 2-3 hours and then cooled to room temperature in the furnace to allow the coating to crystallize and solidify and form a metallurgical bond with the titanium substrate. The thin substrate can avoid thermal stress warping under controlled heating and cooling and the support of the ceramic carrier plate.

[0057] The tin-antimony-based modified coating was prepared by thermal decomposition using a SnO2-Sb-Nb ternary coating with a Sn:Sb:Nb molar ratio of 90:5:5 and a coating thickness of 2.0-4.0 μm. It was applied in 3-4 coats, dried at 120℃ for 10 min after each coat, and finally sintered at 580-600℃ for 1 h. The specific preparation steps for the anode component with the tin-antimony-based modified coating are as follows: N1. Titanium-based pretreatment: Take a pure titanium plate with a thickness of 0.1-0.3 mm, mechanically grind it, immerse it in a 10-15 wt% NaOH solution, and keep it at 60-80℃ for 30-60 min to remove organic stains; then transfer it to a 10% oxalic acid solution and etch it in a 95℃ constant temperature water bath for 1.5-2 h to form micron-level roughness; ultrasonically clean it with deionized water for 10 min, and dry it at 80℃ for later use; N2. Preparation of precursor solution: Weigh tin salt, antimony salt, and niobium salt according to the Sn:Sb:Nb molar ratio of 90:5:5, dissolve them in anhydrous ethanol, add 2 mL of concentrated hydrochloric acid (37%) or acetylacetone as a hydrolysis inhibitor, stir until clear and transparent, and let stand to age to obtain the precursor coating solution; the tin salt, antimony salt, and niobium salt are tin chloride, antimony trichloride, and niobium chloride, respectively.

[0058] N3. Coating and drying: The pretreated titanium base is uniformly coated with the precursor solution by brushing or dip coating, and then placed in an oven at 120℃ for 10 minutes to dry to form a dense dry film. N4. Multiple coating accumulation: Repeat step N3 for 3-4 coating-drying cycles to accumulate a dry film with an oxide coating thickness of 2.0-4.0 μm after sintering. N5. High-temperature sintering: The coated electrode is placed on a ceramic carrier plate and heated to 580-600℃ at a rate of 3-5℃ / min. The temperature is maintained for 1 hour to allow the metal salt to decompose and oxidize thermally. The electrode is then cooled to room temperature in the furnace to form a SnO2-Sb-Nb composite oxide coating.

[0059] The anode component forms a multi-element composite coating by doping with rare earth or transition metals, which reduces the overpotential for active oxygen generation and improves the overall efficiency and stability of active oxygen generation.

[0060] The anode component of this embodiment can achieve bifunctional catalysis under different potential control. It can catalyze the generation of reactive oxygen species and further activate reactive oxygen species intermediates in the system, thereby achieving the synergistic generation of multiple reactive oxygen species. It also has high catalytic efficiency and strong stability.

[0061] The cathode assembly uses hydrophobic carbon paper as its substrate, which has undergone hydrophobic modification. The hydrophobic modification method involves coating the catalyst layer surface with a PTFE emulsion (60% solid content) at a coating amount of 0.1-0.2 mg / cm³. 2 After sintering, a stable critical reaction interface is formed; The catalyst layer is a carbon-based supported Cu-Mn bimetallic catalyst or a nitrogen-doped carbon-graphene composite catalyst layer.

[0062] Among them, the carbon-based supported Cu-Mn bimetallic catalyst has a Cu:Mn molar ratio of 1:2 and a total catalyst loading of 0.3-0.5 mg / cm³. 2 The carbon-based supported Cu-Mn bimetallic catalyst was prepared by loading using a drop-coating method and then sintering at 300℃ in an inert atmosphere for 2 hours. The specific preparation steps are as follows: P1. Carbon paper pretreatment: Cut the hydrophobic carbon paper to the required size, clean it with anhydrous ethanol and deionized water by ultrasonication for 10 minutes each, and dry it at 80℃ for later use.

[0063] P2. Preparation of Catalyst Layer Slurry: Weigh copper nitrate and manganese nitrate according to a Cu:Mn molar ratio of 1:2, dissolve in deionized water, and add Cabot carbon black VULCAN XC72R as a carbon support. Disperse ultrasonically. Slowly add sodium carbonate solution until pH=9-10 to precipitate. Filter, wash, and dry, then heat-treat at 300℃ under nitrogen atmosphere for 2 hours to obtain a carbon-supported Cu-Mn catalyst. Take the catalyst powder, add a 1:1 volume ratio of isopropanol / water mixed solvent, add citric acid or PVP as a dispersant, and ultrasonically disperse to form a uniform slurry.

[0064] P3, Supported Catalyst Layer: The catalyst slurry is uniformly coated onto the surface of carbon paper using a drop-coating method, with the total catalyst loading controlled at 0.3-0.5 mg / cm², and the solvent is evaporated by heating at 80℃.

[0065] P4. Hydrophobic modification of the catalyst layer surface: Dilute the PTFE emulsion (60% solid content) with isopropanol to a solid content of 5%-10%. Apply the diluted PTFE emulsion evenly to the surface of the loaded catalyst layer using a spraying or brushing method. The coating amount is 0.1-0.2 mg / cm² based on pure PTFE. Allow to air dry at room temperature.

[0066] P5. Sintering: Place the above electrodes in a tube furnace, introduce inert gas (nitrogen or argon), raise the temperature to 300°C at 5°C / min, and sinter at that temperature for 2 hours to form a stable hydrophobic microporous interface on the surface of the PTFE catalyst layer.

[0067] The nitrogen-doped carbon-graphene composite catalyst layer has a graphene doping amount of 5%-10% (mass ratio) and a catalyst layer thickness of 50-80 μm. After coating, it undergoes a second sintering process (200℃ / 1h + 350℃ / 2h) to form the final product. The specific preparation steps of the nitrogen-doped carbon-graphene composite catalyst layer are as follows: Q1. Take hydrophobic carbon paper substrate, and ultrasonically clean it with organic solvent and deionized water in sequence to remove surface processing residues. Dry it at 60-80℃ for later use. Q2. Weigh out pre-synthesized nitrogen-doped carbon powder (the product obtained by pyrolysis of urea and carbon source) and graphene powder according to 5%-10% of the graphene mass, and add them to a mixed solvent composed of deionized water, isopropanol and perfluorosulfonic acid resin solution, wherein the solid content of the perfluorosulfonic acid resin solution accounts for 5%-10% of the total mass of the catalyst. Disperse the mixture ultrasonically for 2-3 hours to obtain a uniform catalyst slurry, and control the solid content of the slurry at 15%-25%. Q3. Apply the catalytic slurry evenly to the surface of the carbon paper by scraping or spraying. By controlling the amount of slurry and the coating rate, the coating thickness after drying is maintained at 50-80μm. Allow the paper to stand at room temperature for pre-drying to allow the solvent to evaporate initially. Q4. Place the coated electrode in a heat treatment device, first keep it at 200℃ for 1 hour to remove residual solvent and perform preliminary cross-linking of binder, then raise the temperature to 350℃ and keep it at 2 hours to fully melt and solidify the binder and form a through-pore network. After cooling, a nitrogen-doped carbon-graphene catalyst layer with a complete structure is obtained. Q5. Dilute the PTFE emulsion with a solid content of 60% with deionized water to a suitable coating viscosity, and coat it evenly on the surface of the catalyst layer obtained in step Q4. Control the PTFE solid coating amount to be 0.1-0.2 mg / cm², and air dry at room temperature. Q6. Place the PTFE-coated components in an environment of 340-360℃ for sintering for 10-15 minutes to melt the PTFE particles and form a continuous hydrophobic microporous layer on the outer surface of the catalyst layer, thus constructing a stable gas-liquid-solid three-phase reaction interface.

[0068] The cathode assembly employs bimetallic catalysis or graphene composite modification to significantly suppress hydrogen evolution side reactions and improve the selectivity and generation rate of reactive oxygen species generated by oxygen reduction.

[0069] A method for controlling an electrochemical in-situ reactive oxygen species generator, comprising the electrochemical in-situ reactive oxygen species generator as described above, the method comprising the following steps: S1. The cathode assembly 6 is connected to the DC power supply assembly, and the anode assembly is connected to the dual-mode power supply; the dual-mode power supply has DC power supply and pulse power supply modes. S2. When the cathode component 6 is connected to the DC voltage of the DC power supply component and the anode component 5 is connected to the DC voltage of the dual-mode power supply, the cathode component 6 and the anode component 5 cooperate to undergo an electrochemical reaction to generate the first active oxygen species. S3. When the cathode component 6 is connected to the DC voltage of the DC power supply component and the anode component 5 is connected to the pulse voltage of the dual-mode power supply, the anode component 5 uses the transient high potential generated by the pulse voltage to further convert the first active oxygen species or its intermediate in the liquid into a second active oxygen species with a higher redox potential.

[0070] The control method of this invention ensures the basic oxygen reduction reaction by using cathode DC power supply and switches between anode DC / pulse dual modes to regulate the reaction path, thereby achieving the steady-state generation of the first active oxygen species and the directional conversion to the second active oxygen species with a high oxidation potential. While adapting to different water qualities and washing conditions, it improves the gradient yield and oxidation capacity of active oxygen, and balances the sterilization and purification efficiency with the operating energy consumption.

[0071] When a constant DC voltage is applied to both the anode and cathode, the device is in steady-state electrolysis oxygen production mode.

[0072] Cathode assembly: Dissolved oxygen undergoes a two-electron reduction reaction (O2 + 2H+) on the surface of the gas diffusion electrode. + +2e - →H2O2), which generates hydrogen peroxide in situ.

[0073] Anode assembly: At high oxygen evolution potential, the titanium-based catalytic electrode generates hydroxyl radicals through surface catalytic active sites.

[0074] The products at this stage are mainly long-lasting active oxygen molecules (such as H2O2), which can maintain the basic disinfection and bleaching concentration in the washing liquid.

[0075] In traditional DC electrolysis, a stable diffusion layer easily forms on the anode surface, making it difficult for reactants (such as H2O2) to reach the electrode surface. The generated active groups are also prone to over-oxidation on the electrode, escaping as O2 and wasting electrical energy. The pulse interval of this invention helps to rebalance the diffusion layer on the anode surface, breaking the concentration polarization caused by charge accumulation. This allows the next pulse to break the chemical bonds of intermediate molecules with higher efficiency, generating species with oxidizing power far stronger than ordinary H2O2.

[0076] Specifically, when the anode switches to a pulsed voltage, a high-intensity electric field is rapidly established on the electrode surface, forcibly pulling intermediates such as H2O2 in the solution to accumulate on the anode surface, where they are further oxidized at the electrode / solution interface. H2O2 or dissolved oxygen generated in DC mode, acting as "reactive oxygen intermediates," is rapidly stripped of electrons or oxidized by holes by the strong electric field on the anode surface under the high instantaneous potential of the pulse. The steep rising edge of the pulse waveform generates extremely high instantaneous current density, inducing the production of highly oxidizing species with higher energy and extremely short lifespans, such as hydroxyl radicals, ozone (O3), superoxide radicals, or even more reactive singlet oxygen. 1 O2.

[0077] When the electric field disappears, the reactants adsorbed on the electrode surface rapidly desorb and diffuse into the solution. The "adsorption-reaction-desorption" cycle greatly disrupts the concentration boundary layer on the anode surface, enhances mass transfer efficiency, and significantly increases the activation rate of H2O2 and the generation rate of strong oxidizing species such as hydroxyl radicals.

[0078] Specifically, if the washing water or electrode coating contains trace amounts of transition metal ions, the pulsed voltage can activate the electro-Fenton reaction. When the voltage is applied, H2O2 is continuously generated at the cathode; simultaneously, a small amount of metal ions dissolve at the anode. When the voltage is deactivated, the Fenton reaction between H2O2 and the metal ions in the solution forms a homogeneous activation. The interval between pulses allows sufficient reaction time for the homogeneous reaction in the liquid phase, thus unleashing extremely strong oxidizing power.

[0079] Specifically, when the cathode assembly is connected to a DC voltage and the anode assembly is switched to pulse voltage power supply, the pulse electric field periodically changes the state of the double electric layer and the boundary layer concentration distribution on the anode surface, promoting the conversion of primary reactive oxygen intermediates in the liquid phase into reactive oxygen species with high oxidation potential, while inhibiting the formation of passivation layer on the electrode surface, thereby improving the steady-state yield and oxidation capacity of reactive oxygen species.

[0080] For step S1, the cathode assembly is connected to a high-precision DC power supply (accuracy ±0.01V), which can stably provide the oxygen reduction reaction potential; the anode is connected to a programmable pulsed DC dual-mode power supply, which can switch between DC and pulse modes as needed to achieve flexible control of the regular or efficient generation of reactive oxygen species; users can switch manually to adapt to different application scenarios, or they can switch remotely, such as through a program APP, Bluetooth control, etc.

[0081] For the conventional generation mode, both the anode and cathode components are powered by DC and operate according to the voltage parameters for "conventional generation of active oxygen". The amount of active oxygen generated is stable and the energy consumption is low, making it suitable for conventional scenarios such as purification of lightly polluted water and daily sterilization.

[0082] For the high-efficiency generation mode: the cathode component uses DC power supply and the anode component uses pulse power supply, and operates according to the voltage parameters of "high-efficiency generation of active oxygen", which improves the amount of active oxygen generated and oxidation activity, and is suitable for high-demand scenarios such as degradation of highly polluted water bodies and sterilization of highly resistant microorganisms.

[0083] For steps S2 and S3, the basic power supply voltage parameters are divided into conventional and high-efficiency generation modes to adapt to different reactive oxygen demand.

[0084] When the dual-mode power supply is in DC mode, active oxygen is generated normally. Applicable scenarios include routine water purification and basic sterilization. It can ensure a stable basic supply of active oxygen. The DC voltage of the cathode component is -0.3~-0.5V; the DC voltage of the anode component is 1.3~1.6V.

[0085] When the dual-mode power supply is in pulse mode, active oxygen is generated efficiently. Applicable scenarios include treatment of highly polluted water bodies and efficient sterilization. It can improve the amount of active oxygen generated and oxidation activity. The cathode DC voltage is -0.4~-0.6V, and the cathode is powered by a constant power supply to ensure the basic oxygen reduction reaction. The anode pulse voltage is 2.0~2.5V, with a pulse frequency of 50-80Hz and a duty cycle of 35%-45%.

[0086] In addition, the conductivity of the water body can be fine-tuned to ensure the stable generation of reactive oxygen species. Specifically, in step S4, the voltage is dynamically adjusted by adapting the conductivity of the medium.

[0087] Specifically, for conventional water bodies with a conductivity of 50-200 μS / cm, the operation should be carried out according to the above-mentioned basic voltage parameters; For water bodies with low conductivity (water conductivity < 50 μS / cm): increase the cathode voltage by 0.1~0.2V and the anode voltage by 0.1V. Specifically, the cathode DC voltage is -0.2~-0.4V, the anode DC voltage is 1.4~1.7V, and the anode pulse voltage is 2.1~2.6V. For water bodies with high conductivity (conductivity > 200 μS / cm), the cathode voltage is reduced by 0.1V and the anode voltage is reduced by 0.1~0.2V. Specifically, the cathode DC voltage is -0.4~-0.7V, the anode DC voltage is 1.2~1.5V, and the anode pulse voltage is 1.9~2.4V.

[0088] like Figure 3 , Figure 4 , Figure 6 and Figure 8The device for generating reactive oxygen species in situ using electrochemical methods is shown. The cathode assembly 6 is provided with a water-permeable hole 61. The anode assembly 5 and the cathode assembly 6 extend along the central axis of the second housing 4. The reaction chamber 2 includes an anode assembly space 50 formed on the inner wall of the anode assembly 5 and the second housing 4, and a cathode assembly space 60 located between the inner wall of the cathode assembly 6 and the second housing 4. The reaction space 8 is located between the anode assembly space 50 and the cathode assembly space 60. The side opening 411 includes an anode assembly space side opening 501 communicating with the side of the anode assembly space 50 and a cathode assembly space side opening 601 communicating with the side of the cathode assembly space 60. The bottom opening 412 includes an anode assembly space bottom opening 502 communicating with the bottom of the anode assembly space 50 and a cathode assembly space bottom opening 602 communicating with the bottom of the cathode assembly space 60.

[0089] Specifically, the permeable holes allow liquid to pass through the cathode assembly, increasing the longitudinal flow of the reaction liquid between the anode and cathode, which helps to reduce concentration polarization on the electrode surface.

[0090] In this embodiment, the anode and cathode components extend along the central axis of the second housing, allowing external liquid to enter the anode and cathode component spaces independently, respectively. Since the anode component lacks permeable holes, liquid entering the anode component space cannot enter the reaction space; it can only remain within that space before being discharged through the original opening. Liquid entering the cathode component space, however, can enter the reaction space through the permeable holes of the cathode component, participate in the electrochemical reaction, and then return to the cathode component space and be discharged through the permeable holes. The relatively lower flow rate of the liquid within the reaction space helps to prolong the contact time between dissolved oxygen and other reactants and the electrode surface. The bottom opening maintains fluid continuity within the internal space under different rotation angles and water levels. This invention maintains the uniformity and stability of reactant supply under dynamic operating conditions, improving the efficiency of active oxygen preparation and the operational reliability of the device.

[0091] When the drum rotates, the washing water is subjected to centrifugal force, creating a dynamic pressure difference at the openings on the side and bottom of the second shell. The liquid enters the corresponding chambers through the side and bottom openings of the anode and cathode assembly spaces, respectively. The liquid entering the anode assembly space is blocked by the solid anode assembly, making it difficult to penetrate directly or flow laterally into the inter-electrode region. After forming a directional flow in the cavity, it is discharged along the original path through the corresponding opening. The liquid entering the cathode assembly space passes through the cathode assembly water permeable hole into the 1-3mm reaction space, where mass exchange and electrochemical conversion take place in the narrow slit cavity. Driven by pressure fluctuations and concentration gradients inside and outside the cavity, the reacted liquid flows back to the cathode assembly space through the cathode water permeable hole and is finally discharged through the side or bottom opening along with the liquid in that cavity. This flow path design allows the reaction space to be connected to the outside only through the cathode water permeable hole. The anode assembly space independently undertakes the functions of fluid buffering and pressure equalization, effectively preventing the washing water from directly short-circuiting through the inter-electrode area without reaction. At the same time, the directional guidance of the inlet and outlet paths and the changes in chamber pressure difference extend the effective residence time of the reaction liquid on the electrode surface, ensuring dissolved oxygen mass transfer efficiency while reducing the risk of impurity intrusion and improving the operational stability of the device under dynamic conditions.

[0092] In this embodiment, the anode assembly adopts a non-porous structure, forming a physical barrier to the washing liquid entering the anode assembly space. This prevents the liquid in the cavity from directly penetrating or flowing laterally into the reaction space area, instead discharging through corresponding openings. This avoids the reaction liquid flowing out directly via a short circuit without electrochemical conversion. The liquid in the reaction space is mainly supplied unidirectionally through the cathode permeable holes. Combined with the 1-3mm narrow slit structure between the electrodes, this effectively extends the residence time of the reactants on the electrode surface. Simultaneously, under the turbulent flow conditions generated by the rotation of the washing machine drum, the water entering the anode assembly space is blocked, forming a stable dynamic pressure water cushion. This effectively mitigates the direct scouring of the extremely narrow reaction space by the high-speed water flow and intercepts impurities such as clothing fibers, reducing the risk of electrode surface damage and reaction channel blockage, thus ensuring the structural reliability of the device. Furthermore, this unilateral liquid inlet path confines the electrochemical reaction area to the area between the cathode permeable holes and the anode surface, making the electric field distribution and mass transfer process between the electrodes more concentrated, reducing ineffective bypass current loss, and helping to improve current efficiency and the steady-state yield of active oxygen.

[0093] Example 1 Assembly method of an electrochemical in-situ active oxygen generator Electrode assembly: Insert the anode assembly 5 and the cathode assembly 6 into the fifth limiting groove 48 and the sixth limiting groove 49 inside the second housing 4, respectively. Then, align the anode assembly 5 with the first limiting groove 701 and the third limiting groove 703 of the first housing 3, and align the cathode assembly 6 with the second limiting groove 702 and the fourth limiting groove 704 of the first housing 3, so that the cathode assembly 6 is aligned with the cathode mark and the anode assembly 5 is aligned with the anode mark, to prevent the electrode polarity from being reversed.

[0094] Align the first peripheral limiting extension 71 of the first housing 3 with the first positioning connecting groove 46 of the second housing 4, align the third limiting extension 73 with the second positioning connecting groove 47, align the first extension end connecting groove 74 with the first positioning extension 44, and align the second extension end connecting groove 75 with the second positioning extension 45. Smoothly cover the housing, ensuring the extension area of ​​the first positioning extension 44 is smaller than that of the second positioning extension 45. Use an ultrasonic jig to fuse the interface between the first positioning extension 44 and its corresponding first extension end connecting groove 74, thus fusing the second housing 4 and the first housing 3. Place the sealing ring 9 into the sealing groove of the first housing 3, ensuring the sealing groove is clean and free of impurities, and the sealing ring fits snugly without wrinkles. Fix the generating device to the bottom or side wall of the washing machine tub using connecting components.

[0095] Example 2 In-situ preparation and performance testing of reactive oxygen species The substrate of the anode assembly is a pure titanium plate with a thickness of 0.2 mm; its coating includes a TiO2-based modified coating; as described above, the preparation method of the anode assembly with the TiO2-based modified coating is as follows: M1. Titanium-based pretreatment: Take a pure titanium plate with a thickness of 0.2mm, remove the surface oxide film by mechanical grinding, and then perform alkaline washing and acid etching treatment in sequence, followed by deionized water cleaning and drying. M2, Sol preparation: Tetrabutyl titanate as titanium source and lanthanum nitrate hexahydrate as lanthanum source were dissolved in anhydrous ethanol at a molar ratio of 1.0% for La / (La+Ti). Acetylacetone was added as a complexing agent. After stirring, deionized water was added dropwise for hydrolysis. After aging for 24 hours, La-doped TiO2 sol was obtained. M3. Coating and Drying: The pretreated titanium base is immersed in the sol and pulled at a uniform speed of 2 mm / s and an ambient humidity of 40%. After pulling, it is dried at 90°C for 5 min to form a single-layer gel film. M4, Multilayer Accumulation: Repeat step M3 for 6 coating-drying cycles. After every 2 coatings, perform intermediate heat treatment at 300℃ for 10 minutes to accumulate the coating thickness to 2.0μm. M5. Final sintering: The coated electrode is placed on a ceramic carrier plate and heated to 550°C at a rate of 3°C / min. The temperature is maintained for 2 hours and then cooled to room temperature in the furnace to allow the coating to crystallize and solidify, forming a metallurgical bond with the titanium substrate.

[0096] The cathode assembly uses hydrophobic carbon paper as its substrate and a carbon-based supported Cu-Mn bimetallic catalyst as its catalyst layer.

[0097] The specific preparation steps of the carbon-based supported Cu-Mn bimetallic catalyst are as follows: P1. Carbon paper pretreatment: Cut the hydrophobic carbon paper to the required size, clean it with anhydrous ethanol and deionized water by ultrasonication for 10 minutes each, and dry it at 80℃ for later use.

[0098] P2. Preparation of Catalyst Layer Slurry: Weigh copper nitrate and manganese nitrate according to a Cu:Mn molar ratio of 1:2, dissolve in deionized water, and add Cabot carbon black VULCAN XC72R as a carbon support. Disperse using ultrasound. Slowly add sodium carbonate solution until pH=9 to precipitate. Filter, wash, and dry the precipitate, then heat-treat at 300℃ under nitrogen atmosphere for 2 hours to obtain a carbon-supported Cu-Mn catalyst. Take this catalyst powder, add a 1:1 volume ratio of isopropanol / water mixed solvent, add PVP as a dispersant, and ultrasonically disperse to form a uniform slurry.

[0099] P3, Supported Catalyst Layer: The catalyst slurry is uniformly coated onto the surface of carbon paper using a drop-coating method, with the total catalyst loading controlled at 0.4 mg / cm², and the solvent is evaporated by heating at 80°C.

[0100] P4. Hydrophobic modification of the catalyst layer surface: Dilute the PTFE emulsion (60% solid content) with isopropanol to a solid content of 10%. Apply the diluted PTFE emulsion evenly to the surface of the loaded catalyst layer using a brush coating method. The coating amount is 0.15 mg / cm² based on pure PTFE. Allow to air dry at room temperature.

[0101] P5. Sintering: Place the above electrodes in a tube furnace, introduce inert gas (nitrogen or argon), raise the temperature to 300°C at 5°C / min, and sinter at that temperature for 2 hours to form a stable hydrophobic microporous interface on the surface of the PTFE catalyst layer.

[0102] Test conditions: The assembled generating device is immersed in a container filled with 1L of tap water medium. The tap water has a pH of 7.2, a conductivity of 100μS / cm, and a total dissolved chlorine of 0.6mg / L. An external 12V DC power supply or an external programmable DC power supply is connected. The cathode assembly 6 is connected to the DC power supply assembly, and the anode assembly 5 is connected to the dual-mode power supply. The medium circulates in the container at a flow rate of 400mL / min. The rotating device simulates the dynamic water flow scouring conditions generated by the rotation of a washing machine drum. The water flow in the container forms a dynamic flow around the generating device. Specifically, the generating device is fixed on the inner wall of the container or a special support. The liquid in the container generates relative flow through the oscillation and rotation of the container body by a magnetic stirrer, stirring paddle, circulating pump, or the container body. The relative linear velocity between the liquid and the surface of the device is controlled to be equivalent to the scouring state when the washing machine drum is rotating. The rotation speed is 60rpm, the circulation reaction is 60min, and the parallel test is performed 6 times. For the first 30 minutes, a conventional generation mode is used, with both the anode and cathode components powered by DC. The DC voltage of the cathode component is -0.4V, and the DC voltage of the anode component is 1.4V. For the next 30 minutes, a high-efficiency generation mode is used: the cathode component is powered by DC, and the anode component is powered by pulse. The DC voltage of the cathode is -0.5V, and the constant power supply to the cathode ensures the basic oxygen reduction reaction. The pulse voltage of the anode is 2.2V, with a pulse frequency of 60Hz and a duty cycle of 40%.

[0103] Detection methods: The contents of hydrogen peroxide and hydroxyl radicals in the reaction medium were quantitatively detected by spectrophotometry and electron spin resonance (ESR) combined with spin trapping technology. Table 1. Detection data of reactive oxygen species generation process

[0104] Test results: After 6 parallel tests, the concentration of active oxygen in the medium was stable, and the average amount generated met the actual needs of various oxidation and sterilization treatments, proving that this device can efficiently and stably prepare active oxygen in situ with excellent preparation effect.

[0105] Example 3 The difference between Example 3 and Example 2 is that the substrate of the anode component is a pure titanium plate with a thickness of 0.2 mm; and its coating is a tin-antimony-based modified coating.

[0106] The specific preparation steps for the anode assembly with a tin-antimony-based modified coating are as follows: N1. Titanium-based pretreatment: Take a pure titanium plate with a thickness of 0.2mm, remove the surface oxide film by mechanical grinding, and then perform alkaline washing and acid etching treatment in sequence, followed by deionized water cleaning and drying. N2. Preparation of precursor solution: Weigh tin salt, antimony salt, and niobium salt according to the Sn:Sb:Nb molar ratio of 90:5:5, dissolve them in anhydrous ethanol, add 2 mL of concentrated hydrochloric acid (37%) as a hydrolysis inhibitor, stir until clear and transparent, and let stand to age to obtain precursor coating solution; tin salt, antimony salt, and niobium salt are tin chloride, antimony trichloride, and niobium chloride, respectively.

[0107] N3. Coating and drying: The pretreated titanium base is uniformly coated with the precursor solution by brushing or dip coating, and then placed in an oven at 120℃ for 10 minutes to dry to form a dense dry film. N4. Multiple coating accumulation: Repeat step N3 for 4 coating-drying cycles to accumulate a dry film with an oxide coating thickness of 3.0 μm after sintering. N5. High-temperature sintering: The coated electrode is placed on a ceramic carrier plate and heated to 600℃ at 5℃ / min. The temperature is maintained for 1 hour to allow the metal salt to decompose and oxidize thermally. The electrode is then cooled to room temperature in the furnace to form a SnO2-Sb-Nb composite oxide coating.

[0108] The cathode assembly uses hydrophobic carbon paper as its substrate and nitrogen-doped carbon-graphene composite catalyst layer as its catalyst layer.

[0109] The specific preparation steps of the nitrogen-doped carbon-graphene composite catalyst layer are as follows: Q1. Take hydrophobic carbon paper substrate, and ultrasonically clean it with ethanol solvent and deionized water in sequence to remove surface processing residues. Dry it at 60-80℃ for later use. Q2. Weigh out 10% of the pre-synthesized nitrogen-doped carbon powder (the product obtained by pyrolysis of urea and carbon source) and graphene powder, and add them to a mixed solvent composed of deionized water, isopropanol and perfluorosulfonic acid resin solution, wherein the solid content of the perfluorosulfonic acid resin solution accounts for 5% of the total mass of the catalyst. Disperse the mixture ultrasonically for 2-3 hours to obtain a uniform catalytic slurry, and control the solid content of the slurry at 15%-25%. Q3. Apply the catalytic slurry evenly to the surface of the carbon paper by scraping or spraying. By controlling the amount of slurry and the coating rate, the coating thickness after drying is maintained at 60μm. Allow the paper to stand at room temperature for pre-drying to allow the solvent to evaporate initially. Q4. Place the coated electrode in a heat treatment device, first keep it at 200℃ for 1 hour to remove residual solvent and perform preliminary cross-linking of binder, then raise the temperature to 350℃ and keep it at 2 hours to fully melt and solidify the binder and form a through-pore network. After cooling, a nitrogen-doped carbon-graphene catalyst layer with a complete structure is obtained. Q5. Dilute the PTFE emulsion with 60% solid content with deionized water to a suitable coating viscosity, and coat it evenly on the surface of the catalyst layer obtained in step Q4. Control the PTFE solid coating amount to be 0.15 mg / cm², and air dry at room temperature. Q6. Place the PTFE-coated component in a 350℃ environment for sintering for 15 minutes to melt the PTFE particles and form a continuous hydrophobic microporous layer on the outer surface of the catalyst layer, thus constructing a stable gas-liquid-solid three-phase reaction interface.

[0110] Test conditions: The assembled generating device is immersed in a container filled with 1L of tap water medium. The tap water has a pH of 7.2, a conductivity of 100μS / cm, and a total dissolved chlorine of 0.6mg / L. An external 12V DC power supply or an external programmable DC power supply is connected. The cathode assembly 6 is connected to the DC power supply assembly, and the anode assembly 5 is connected to the dual-mode power supply. The medium circulates in the container at a flow rate of 400mL / min. The rotating device simulates the dynamic water flow scouring conditions generated by the rotation of a washing machine drum. The water flow in the container forms a dynamic flow around the generating device. Specifically, the generating device is fixed on the inner wall of the container or a special support. The liquid in the container generates relative flow through the oscillation and rotation of the container body by a magnetic stirrer, stirring paddle, circulating pump, or the container body. The relative linear velocity between the liquid and the surface of the device is controlled to be equivalent to the scouring state when the washing machine drum is rotating. The rotation speed is 60rpm, the circulation reaction is 60min, and the parallel test is performed 6 times. For the first 30 minutes, a conventional generation mode is used, with both the anode and cathode components powered by DC. The DC voltage of the cathode component is -0.4V, and the DC voltage of the anode component is 1.4V. For the next 30 minutes, a high-efficiency generation mode is used: the cathode component is powered by DC, and the anode component is powered by pulse. The DC voltage of the cathode is -0.5V, and the constant power supply to the cathode ensures the basic oxygen reduction reaction. The pulse voltage of the anode is 2.2V, with a pulse frequency of 60Hz and a duty cycle of 40%.

[0111] Detection methods: The contents of hydrogen peroxide and hydroxyl radicals in the reaction medium were quantitatively detected by spectrophotometry and electron spin resonance (ESR) combined with spin trapping technology. Table 2. Detection data of reactive oxygen species generation process

[0112] Example 2 uses a titanium dioxide-modified anode paired with a copper-manganese bimetallic catalytic cathode. Under conventional DC power supply conditions, the electrochemical reaction is mild and stable, with high selectivity for hydrogen peroxide generation and low susceptibility to excessive oxidation side reactions. This is more suitable for applications requiring stable production of reactive oxygen species under conventional modes. However, in high-efficiency pulsed mode, the titanium dioxide coating in Example 2 exhibits limited voltage resistance and strong oxidation activation capabilities, resulting in weak interfacial response under the pulsed electric field. It can only slightly increase free radical production and cannot efficiently cleave reactive oxygen species intermediates, thus providing a weak enhancement effect. Example 3 uses a tin-antimony-based modified high-energy oxidation anode and a nitrogen-doped carbon-graphene composite cathode. Under conventional DC power supply conditions, the tin-antimony anode has stronger intrinsic oxidation capabilities and will decompose a small amount of hydrogen peroxide generated in the system under DC conditions. Although the H2O2 yield is slightly lower under DC mode, the mass transfer efficiency and activation capability of the nitrogen-doped graphene under high-voltage pulses compensate for this deficiency, thereby improving the final disinfection effect. Due to its excellent electrical conductivity and high voltage withstand capability, the tin-antimony-based anode can withstand high-frequency high-voltage pulses in the high-efficiency reaction mode of anode pulse power supply. Under the strong electric field, it efficiently activates water molecules and hydrogen peroxide intermediates, generating a large number of highly active and strong oxidizing species such as hydroxyl radicals. The nitrogen-doped carbon-graphene composite cathode can quickly match the charge fluctuations of the pulse electric field, improve mass transfer efficiency, and synergistically enhance the overall oxidation and sterilization capabilities. At the same time, under pulse conditions, hydrogen peroxide, as a precursor, is directionally converted and consumed, and the content of hydroxyl radicals is greatly increased. This can enhance the efficiency of interfacial charge transfer and activation of reactive oxygen intermediates, effectively increasing the generation of strong oxidizing radicals, resulting in better high-efficiency oxidation and sterilization purification performance.

[0113] Example 4 The difference between Example 4 and Example 2 is that, When the water conductivity is <50μS / cm, the cathode voltage is increased by 0.1~0.2V and the anode voltage is increased by 0.1V. Specifically, the cathode DC voltage is -0.2~-0.4V, the anode DC voltage is 1.4~1.7V, and the anode pulse voltage is 2.1~2.6V. Specifically, the test conditions were as follows: The assembled generating device was immersed in a container filled with 1L of tap water medium. The tap water had a pH of 7.2, a conductivity of 40μS / cm, and a total dissolved chlorine concentration of 0.6mg / L. An external 12V DC power supply or an external programmable DC power supply was connected. The cathode assembly 6 was connected to the DC power supply assembly, and the anode assembly 5 was connected to the dual-mode power supply. The medium circulated in the container at a flow rate of 400mL / min. The generating device rotated in the container in coordination with a rotating device at a speed of 60rpm. The cyclic reaction lasted for 60min, and the test was repeated 6 times in parallel. For the first 30 minutes, a conventional generation mode is used, with both the anode and cathode components powered by DC. The DC voltage of the cathode component is -0.3V, and the DC voltage of the anode component is 1.5V. For the next 30 minutes, a high-efficiency generation mode is used: the cathode component is powered by DC, and the anode component is powered by pulse. The DC voltage of the cathode is -0.4V, and the constant power supply to the cathode ensures the basic oxygen reduction reaction. The pulse voltage of the anode is 2.3V, with a pulse frequency of 60Hz and a duty cycle of 40%.

[0114] Detection methods: The contents of hydrogen peroxide and hydroxyl radicals in the reaction medium were quantitatively detected by spectrophotometry and electron spin resonance (ESR) combined with spin trapping technology. Table 3. Detection data of reactive oxygen species generation process

[0115] Test results: The ohmic impedance of the solution increases under low conductivity. Although the mass transfer is slightly limited after voltage adjustment compensation, the reactive oxygen generation rate is lower than that in Example 2, but the trend is the same, which verifies the effectiveness of the voltage compensation strategy.

[0116] Example 5 The difference between Example 5 and Example 2 is that... Water conductivity > 200 μS / cm; cathode voltage reduced by 0.1V, anode voltage reduced by 0.1~0.2V. Specifically, cathode DC voltage: -0.4~-0.7V, anode DC voltage: 1.2~1.5V, anode pulse voltage: 1.9~2.4V.

[0117] Specifically, the test conditions were as follows: The assembled generating device was immersed in a container filled with 1L of tap water medium. The tap water had a pH of 7.2, a conductivity of 240μS / cm, and a total dissolved chlorine concentration of 0.6mg / L. An external 12V DC power supply or an external programmable DC power supply was connected. The cathode assembly 6 was connected to the DC power supply assembly, and the anode assembly 5 was connected to the dual-mode power supply. The medium circulated in the container at a flow rate of 400mL / min. The generating device rotated in the container in coordination with a rotating device at a speed of 60rpm. The cyclic reaction lasted for 60min, and the test was repeated 6 times in parallel. For the first 30 minutes, a conventional generation mode is used, with both the anode and cathode components powered by DC. The DC voltage of the cathode component is -0.5V, and the DC voltage of the anode component is 1.3V. For the next 30 minutes, a high-efficiency generation mode is used: the cathode component is powered by DC, and the anode component is powered by pulse. The DC voltage of the cathode is -0.6V, and the constant power supply to the cathode ensures the basic oxygen reduction reaction. The pulse voltage of the anode is 2.0V, with a pulse frequency of 60Hz and a duty cycle of 40%.

[0118] Detection methods: The contents of hydrogen peroxide and hydroxyl radicals in the reaction medium were quantitatively detected by spectrophotometry and electron spin resonance (ESR) combined with spin trapping technology. Table 4. Detection data of reactive oxygen species generation process

[0119] Test results: High conductivity reduces solution impedance, and the current density can still be maintained even after voltage reduction. Improved mass transfer makes the reactive oxygen generation rate slightly better than in Example 2, and energy consumption is reduced simultaneously, demonstrating the advantages of adaptive parameter control.

[0120] Example 6 The difference between Example 6 and Example 3 is as follows: When the water conductivity is <50μS / cm, the cathode voltage is increased by 0.1~0.2V and the anode voltage is increased by 0.1V. Specifically, the cathode DC voltage is -0.2~-0.4V, the anode DC voltage is 1.4~1.7V, and the anode pulse voltage is 2.1~2.6V. Specifically, the test conditions were as follows: The assembled generating device was immersed in a container filled with 1L of tap water medium. The tap water had a pH of 7.2, a conductivity of 40μS / cm, and a total dissolved chlorine concentration of 0.6mg / L. An external 12V DC power supply or an external programmable DC power supply was connected. The cathode assembly 6 was connected to the DC power supply assembly, and the anode assembly 5 was connected to the dual-mode power supply. The medium circulated in the container at a flow rate of 400mL / min. The generating device rotated in the container in coordination with a rotating device at a speed of 60rpm. The cyclic reaction lasted for 60min, and the test was repeated 6 times in parallel. For the first 30 minutes, a conventional generation mode is used, with both the anode and cathode components powered by DC. The DC voltage of the cathode component is -0.3V, and the DC voltage of the anode component is 1.5V. For the next 30 minutes, a high-efficiency generation mode is used: the cathode component is powered by DC, and the anode component is powered by pulse. The DC voltage of the cathode is -0.4V, and the constant power supply to the cathode ensures the basic oxygen reduction reaction. The pulse voltage of the anode is 2.3V, with a pulse frequency of 60Hz and a duty cycle of 40%.

[0121] Detection methods: The contents of hydrogen peroxide and hydroxyl radicals in the reaction medium were quantitatively detected by spectrophotometry and electron spin resonance (ESR) combined with spin trapping technology. Table 5. Detection data of reactive oxygen species generation process

[0122] Test results: Example 6 showed excellent cathode conductivity, with pulse response attenuation less than that of Example 4 at low conductivity, and the •OH endpoint concentration still reached 90% of that of Example 3, verifying the adaptability of high conductivity electrode and voltage compensation to low mineralization water quality.

[0123] Example 7 The difference between Example 7 and Example 3 is as follows: Water conductivity > 200 μS / cm; cathode voltage reduced by 0.1V, anode voltage reduced by 0.1~0.2V. Specifically, cathode DC voltage: -0.4~-0.7V, anode DC voltage: 1.2~1.5V, anode pulse voltage: 1.9~2.4V.

[0124] Specifically, the test conditions were as follows: The assembled generating device was immersed in a container filled with 1L of tap water medium. The tap water had a pH of 7.2, a conductivity of 240μS / cm, and a total dissolved chlorine concentration of 0.6mg / L. An external 12V DC power supply or an external programmable DC power supply was connected. The cathode assembly 6 was connected to the DC power supply assembly, and the anode assembly 5 was connected to the dual-mode power supply. The medium circulated in the container at a flow rate of 400mL / min. The generating device rotated in the container in coordination with a rotating device at a speed of 60rpm. The cyclic reaction lasted for 60min, and the test was repeated 6 times in parallel. For the first 30 minutes, a conventional generation mode is used, with both the anode and cathode components powered by DC. The DC voltage of the cathode component is -0.5V, and the DC voltage of the anode component is 1.3V. For the next 30 minutes, a high-efficiency generation mode is used: the cathode component is powered by DC, and the anode component is powered by pulse. The DC voltage of the cathode is -0.6V, and the constant power supply to the cathode ensures the basic oxygen reduction reaction. The pulse voltage of the anode is 2.0V, with a pulse frequency of 60Hz and a duty cycle of 40%.

[0125] Detection methods: The contents of hydrogen peroxide and hydroxyl radicals in the reaction medium were quantitatively detected by spectrophotometry and electron spin resonance (ESR) combined with spin trapping technology. Table 6. Detection data of reactive oxygen species generation process

[0126] Test results: Example 7 combines high conductivity with the high conductivity coating of Example 3. After voltage reduction, ineffective heat loss is avoided. The generation rate of hydroxyl radicals in the pulse stage is improved compared with Example 3. Current efficiency is optimized simultaneously, demonstrating the synergistic effect of matching water quality, electrode and power supply parameters.

[0127] Example 8 The difference between Example 8 and Example 4 is as follows: When the water conductivity is <50μS / cm, the standard water conductivity base voltage parameters of 50-200μS / cm shall be used for operation. The tap water has a pH of 7.2, a conductivity of 40 μS / cm, and a total dissolved chlorine concentration of 0.6 mg / L. The detection method is the same as in Example 4. Table 7. Detection data of reactive oxygen species generation process

[0128] Test results: In Example 4, the yield was higher after the voltage was reduced; in Example 8, no voltage compensation was performed under low conductivity, and the ohmic voltage drop of the solution resulted in insufficient effective cell voltage, and the amount of active oxygen generated decreased by about 30%-35% compared with the baseline, which verifies the necessity of adaptive voltage control.

[0129] Example 9 The difference between Example 9 and Example 5 is as follows: When the water conductivity is greater than 200 μS / cm, the standard water conductivity base voltage parameters of 50-200 μS / cm shall be used for operation. The tap water has a pH of 7.2, a conductivity of 240 μS / cm, and a total dissolved chlorine concentration of 0.6 mg / L. The detection method is the same as in Example 5. Table 8. Detection data of reactive oxygen species generation process

[0130] Test Results: In Example 5, the generation of hydroxyl radicals was significantly increased under pulsed mode after voltage adjustment. In contrast, Example 9, without voltage reduction under high conductivity, experienced rapid hydrogen peroxide accumulation in the conventional DC phase due to high current. However, upon entering the high-efficiency pulsed phase, the excessively high actual cell voltage triggered severe anodic oxygen evolution and cathodic hydrogen evolution side reactions, leading to the ineffective oxidation of hydrogen peroxide into oxygen, thus disrupting the hydroxyl radical generation pathway. At 60 minutes, the hydroxyl radical concentration was only 4.5 μmol / L, far lower than that of Example 5 with voltage reduction optimization, and even significantly lower than that of the baseline Example 2 for conventional water quality. This demonstrates that without voltage reduction under high conductivity, severe side reactions occur, resulting in a significant decrease in current efficiency.

[0131] Example 10 The difference between Example 10 and Example 6 is as follows: When the water conductivity is <50μS / cm, the standard water conductivity base voltage parameters of 50-200μS / cm shall be used for operation. The tap water has a pH of 7.2, a conductivity of 40 μS / cm, and a total dissolved chlorine concentration of 0.6 mg / L. The detection method is the same as in Example 4. Table 9. Detection data of reactive oxygen species generation process

[0132] Test results: In Example 6, the generation of hydroxyl radicals increased under pulse mode after voltage regulation. In Example 10, the advantage of cathode conductivity partially offset the effect of low conductivity, and the decrease in the final concentration of hydroxyl radicals was less than that in Example 2, verifying the adaptability of the high conductivity electrode to a wide range of water quality.

[0133] Example 11 The difference between Example 11 and Example 7 is as follows: When the water conductivity is greater than 200 μS / cm, the standard water conductivity base voltage parameters of 50-200 μS / cm shall be used for operation. The tap water has a pH of 7.2, a conductivity of 240 μS / cm, and a total dissolved chlorine concentration of 0.6 mg / L. The detection method is the same as in Example 5. Table 10. Detection data of reactive oxygen species generation process

[0134] Test Results: In Example 7, the SnO2 anode exhibited superior activation efficiency under pulsed high potential after pressure reduction. In contrast, Example 11, without voltage reduction at a high conductivity of 240 μS / cm, resulted in severe anode oxygen evolution reaction during the pulsed phase due to the extremely strong intrinsic oxidation capacity of the tin-antimony anode, caused by excessively high actual cell voltage. A large amount of hydrogen peroxide precursor was ineffectively oxidized to oxygen and escaped, leading to mass transfer deterioration caused by bubble encapsulation on the electrode surface and disruption of the directional conversion pathway of hydroxyl radicals. At 60 min, the hydroxyl radical concentration was only 8.2 μmol / L, significantly lower than that of Example 7 after pressure reduction optimization and even considerably lower than that of the baseline Example 3 for conventional water quality. This demonstrates that for highly active electrodes, failure to reduce voltage at high conductivity can trigger severe side reactions, leading to a significant decrease in current efficiency.

[0135] Example 12 Based on Example 2, the bactericidal efficacy of the active oxygen prepared by this device was tested. Test objective: To verify the oxidative bactericidal efficacy of the active oxygen generated in situ by this device against highly resistant microorganisms; Test strain: Bacillus subtilis var. niger spores (ATCC 9372), prepared at a concentration of approximately 2.5 × 10⁻⁶. 6 CFU / tablet spore suspension and inoculated onto the carrier; Test method: Immerse the assembled generator in a container filled with 1L of tap water medium. Place the spore-inoculating carrier on the side wall of the container. The tap water has a pH of 7.2, a conductivity of 100 μS / cm, and a total dissolved chlorine concentration of 0.6 mg / L. Connect an external 12V DC power supply or an external programmable DC power supply. The cathode assembly 6 is connected to the DC power supply assembly, and the anode assembly 5 is connected to the dual-mode power supply. The medium circulates in the container at a flow rate of 400 mL / min. The generator rotates in the container via a rotating device at a speed of 60 rpm. Turn on the device and regulate the amount of active oxygen generated by the external power supply for 20 minutes. For the first 10 minutes, use the conventional generation mode, with both the anode and cathode components powered by DC. The DC voltage of the cathode component is -0.4V, and the DC voltage of the anode component is 1.4V. For the last 10 minutes, use the high-efficiency generation mode: the cathode component is powered by DC, and the anode component is powered by pulse. The DC voltage of the cathode is -0.5V, and the constant power supply to the cathode ensures the basic oxygen reduction reaction. The pulse voltage of the anode is 2.2V, with a pulse frequency of 60Hz and a duty cycle of 40%.

[0136] A quantitative bactericidal test was conducted in accordance with the "Disinfection Technical Specifications", with three parallel test groups set up; Test results: After the experiment, the residual viable bacteria counts in the three parallel groups were 1.2 × 10⁻⁶. 5 CFU / tablet, 9.5×10 4 CFU / tablet, 7.9×10 4 CFU / tablet, with kill log values ​​of 1.33KL, 1.42KL, and 1.5KL respectively, and average kill rates of 95.37%, 96.23%, and 96.84% respectively, proves that the active oxygen prepared in situ by this device has extremely strong oxidative bactericidal efficacy and can efficiently remove highly resistant microorganisms, fully demonstrating the advantages of active oxygen oxidation treatment.

[0137] Example 13 Based on Example 3, the bactericidal efficacy of the active oxygen prepared by this device was tested. Test objective: To verify the oxidative bactericidal efficacy of the active oxygen generated in situ by this device against highly resistant microorganisms; Test strain: Bacillus subtilis var. niger spores (ATCC 9372), prepared at a concentration of approximately 2.5 × 10⁻⁶. 6 CFU / tablet spore suspension and inoculated onto the carrier; Test method: Immerse the assembled generator in a container filled with 1L of tap water medium. Place the carrier for inoculating spores on the side wall of the container. The tap water has a pH of 7.2, a conductivity of 100μS / cm, and a total dissolved chlorine of 0.6mg / L. Connect an external 12V DC power supply or an external programmable DC power supply. The cathode assembly 6 is connected to the DC power supply assembly, and the anode assembly 5 is connected to the dual-mode power supply. The medium circulates in the container at a flow rate of 400mL / min. The generator rotates in the container via a rotating device at a speed of 60rpm.

[0138] Turn on the device and regulate the amount of active oxygen generated by the external power supply for 20 minutes. For the first 10 minutes, use the conventional generation mode, with both the anode and cathode components powered by DC. The DC voltage of the cathode component is -0.4V, and the DC voltage of the anode component is 1.4V. For the last 10 minutes, use the high-efficiency generation mode: the cathode component is powered by DC, and the anode component is powered by pulse. The DC voltage of the cathode is -0.5V, and the constant power supply to the cathode ensures the basic oxygen reduction reaction. The pulse voltage of the anode is 2.2V, with a pulse frequency of 60Hz and a duty cycle of 40%.

[0139] A quantitative bactericidal test was conducted in accordance with the "Disinfection Technical Specifications", with three parallel test groups set up; Test results: After the experiment, the residual viable bacteria counts in the three parallel groups were 4.1 × 10⁻⁶. 4 CFU / tablet, 4.0×10 4 CFU / tablet, 3.2×10 4 With an average kill rate of ≥98.3% (CFU / tablet), the active oxygen prepared in situ by this device has extremely strong oxidative bactericidal efficacy and can efficiently remove highly resistant microorganisms, fully demonstrating the advantages of active oxygen oxidation treatment.

[0140] The above examples are merely illustrative of the technical content of the present invention to facilitate easier understanding by the reader, but do not imply that the implementation of the present invention is limited to these examples. Any technical extensions or re-creations made based on the present invention are protected by the present invention. The scope of protection of the present invention is defined by the claims.

Claims

1. An electrochemical in-situ active oxygen generating device, comprising a shell (1), a reaction cavity (2) located in the shell (1), characterized in that: The housing (1) includes a first housing (3) and a second housing (4) that enclose the reaction chamber (2), an anode assembly (5) and a cathode assembly (6) located in the reaction chamber (2). The second housing (4) is provided with a plurality of openings (41) for liquid to pass through. The second housing (4) surrounds the anode assembly (5) and the cathode assembly (6) on the outside. The projection of the second housing (4) is arc-shaped. The cathode assembly (6) is connected to a DC power supply assembly. The anode assembly (5) is connected to a dual-mode power supply. The dual-mode power supply has DC power supply and pulse power supply modes. When the anode assembly (5) is switched to the dual-mode power supply with DC power supply mode, the anode assembly (5) and the cathode assembly (6) work together to generate a first active oxygen species. When the anode assembly (5) is switched to the dual-mode power supply with pulse power supply mode, the anode assembly (5) and the cathode assembly (6) work together to convert the first active oxygen species or its intermediates generated in the liquid into a second active oxygen species with a higher oxidation-reduction potential.

2. The electrochemical in-situ active oxygen generation device according to claim 1, characterized in that: The second housing (4) is columnar, and the opening (41) is circular, elliptical, or polygonal. The second housing (4) is ultrasonically welded to the first housing (3).

3. The electrochemical in-situ active oxygen generation device according to claim 1, characterized in that: The second housing (4) is provided with a second housing opening (42). The opening (41) includes a side opening (411) located on the side of the second housing (4) and a bottom opening (412) located at the bottom of the second housing (4). Both the side opening (411) and the bottom opening (412) are provided in multiples.

4. The electrochemical in-situ active oxygen generator according to claim 1, characterized in that: The first housing (3) is provided with an extension (7) extending toward the second housing (4). The extension (7) is provided with a first peripheral limiting extension (71) on its periphery and a second inner extension (72) on its inner side. The first peripheral limiting extension (71) is provided with a first limiting groove (701) limiting the anode assembly (5) and a second limiting groove (702) limiting the cathode assembly (6). The second inner extension (72) is provided with a third limiting groove (703) limiting the anode assembly (5) and a fourth limiting groove (704) limiting the cathode assembly (6). The first limiting groove (701) and the third limiting groove (703) are located on the same straight line. The second limiting groove (702) and the fourth limiting groove (704) are located on the same straight line. The bottom of the second housing (4) is provided with a fifth limiting groove (48) limiting the anode assembly (5) and a sixth limiting groove (49) limiting the cathode assembly (6).

5. The electrochemical in-situ active oxygen generator according to claim 4, characterized in that: The first peripheral limiting extension (71) includes a first extension end (711), a second extension end (712), and a third extension end (713) located between the first extension end (711) and the second extension end (712). The first limiting groove (701) is located between the first extension end (711) and the third extension end (713). The second limiting groove (702) is located between the second extension end (712) and the third extension end (713). The second inner extension (72) includes a fourth extension end (721), a fifth extension end (722), and a sixth extension end (723) located between the fourth extension end (721) and the fifth extension end (722). The third limiting groove (703) is located between the fourth extension end (721) and the sixth extension end (723). The fourth limiting groove (704) is located between the fifth extension end (722) and the sixth extension end (723).

6. The electrochemical in-situ active oxygen generator according to claim 4, characterized in that: The extension (7) is provided with a plurality of third limiting extensions (73) located on its periphery. A first extension end connecting groove (74) is provided between the third limiting extension (73) and the first periphery limiting extension (71). A second extension end connecting groove (75) is provided between two adjacent third limiting extensions (73). The second housing (4) is provided with a first positioning extension (44) extending into the first extension end connecting groove (74), a second positioning extension (45) extending into the second extension end connecting groove (75), a first positioning connecting groove (46) into which the first periphery limiting extension (71) extends, and a second positioning connecting groove (47) into which the third limiting extension (73) extends.

7. The electrochemical in-situ active oxygen generator according to claim 3, characterized in that: The distance between the anode assembly (5) and the cathode assembly (6) is 1-3 mm. The reaction chamber (2) includes a reaction space (8) located between the anode assembly (5) and the cathode assembly (6). The side opening (411) includes a reaction space side opening (81) communicating with the side of the reaction space (8). The reaction space side opening (81) is provided in two sets and is arranged opposite to each other on both sides of the reaction space (8). The bottom opening (412) includes a reaction space bottom opening (82) communicating with the bottom of the reaction space (8).

8. The electrochemical in-situ active oxygen generator according to claim 5, characterized in that: The anode assembly (5) adopts a titanium-based catalytic electrode, and the cathode assembly (6) adopts a gas diffusion electrode. The first housing (3) is provided with a first slot (31) for the conductive part of the anode assembly (5) to extend out and a second slot (32) for the conductive part of the cathode assembly (6) to extend out. The first slot (31) is located between the first limiting slot (701) and the third limiting slot (703), and the second slot (32) is located between the second limiting slot (702) and the fourth limiting slot (704). The first slot (31) and the second slot (32) are misaligned and opposite to each other.

9. The electrochemical in-situ active oxygen generator according to claim 8, characterized in that: The cathode assembly (6) is provided with a water-permeable hole (61). The anode assembly (5) and the cathode assembly (6) extend along the central axis of the second housing (4). The reaction chamber (2) includes an anode assembly space (50) formed by the inner walls of the anode assembly (5) and the second housing (4) and a cathode assembly space (60) located between the inner walls of the cathode assembly (6) and the second housing (4). The reaction space (8) is located between the anode assembly space (50) and the cathode assembly space (60). The side opening (411) includes an anode assembly space side opening (501) communicating with the side of the anode assembly space (50) and a cathode assembly space side opening (601) communicating with the side of the cathode assembly space (60). The bottom opening (412) includes an anode assembly space bottom opening (502) communicating with the bottom of the anode assembly space (50) and a cathode assembly space bottom opening (602) communicating with the bottom of the cathode assembly space (60).

10. A method for controlling an electrochemical in-situ reactive oxygen generation device, characterized in that: The device for generating reactive oxygen species in situ using electrochemical methods according to any one of claims 1-9, wherein the control method comprises the following steps: S1. The cathode assembly (6) is connected to the DC power supply assembly, and the anode assembly (5) is connected to the dual-mode power supply, which has DC power supply and pulse power supply modes. S2. When the cathode component (6) is connected to the DC voltage of the DC power supply component and the anode component (5) is connected to the DC voltage of the dual-mode power supply, the cathode component (6) and the anode component (5) cooperate to undergo an electrochemical reaction to generate the first active oxygen species. S3. When the cathode component (6) is connected to the DC voltage of the DC power supply component and the anode component (5) is connected to the pulse voltage of the dual-mode power supply, the anode component (5) uses the transient high potential generated by the pulse voltage to further convert the first active oxygen species or its intermediate in the liquid into a second active oxygen species with a higher oxidation-reduction potential.

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