Method for generating active oxygen molecular flow through air source electro-catalysis excitation

Abstract

The invention discloses a method for generating active oxygen molecular flow through air source electro-catalysis excitation. The method comprises the following steps that S1, filtered air is subjected to ultrasonic oscillation to be scattered and recombined, and then the relative humidity of the air is adjusted; or the relative humidity of the filtered air is adjusted, and then the air is scattered and recombined through ultrasonic oscillation; s2, the air is subjected to an electro-catalytic reaction, and active oxygen molecule flow is generated; the conditions of the electro-catalytic reaction are as follows: the anode is a carbon electrode made of a carbon nanotube doped with silver and ruthenium, and the anode has a double-helix structure; the cathode takes foamed nickel-porous graphene as a carrier, and a nickel-cobalt alloy is loaded on the carrier; an electrolyte adopted in the electro-catalysis reaction comprises amino acid and soluble metal salt; pulse type voltage is applied to the electro-catalytic reaction. According to the method, the production efficiency of the active oxygen molecular flow can be remarkably improved, and the produced active oxygen molecular flow can be applied to the fields of environmental protection, medical treatment, material treatment and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalysis, and particularly relates to a method for electrocatalytically exciting an active oxygen molecular flow from an air source. Background Art

[0002] Active oxygen molecules play a key role in many fields. In the field of environmental purification, they can effectively remove various pollutants through oxidation decomposition reactions, realizing the restoration and improvement of the environment; in the medical field, active oxygen, with its strong oxidation ability, can accurately kill bacteria, viruses and other microorganisms, achieving the purpose of efficient disinfection and sterilization, and ensuring the safety of the medical environment; in addition, active oxygen also plays an irreplaceable role in biological research, material surface treatment and other aspects.

[0003] Currently, there are many drawbacks in the traditional methods for generating active oxygen molecules. Chemical methods, such as the reaction of hydrogen peroxide with oxidants such as hypochlorous acid (HClO), can generate singlet oxygen. However, this method relies on a large amount of chemical reagents, not only with high costs, but also generating secondary pollution during use, causing serious harm to the environment; the photocatalytic method is significantly limited by light source conditions, with strict requirements for light intensity, wavelength, etc., and low energy conversion efficiency, making it difficult to achieve large-scale applications; the thermal catalytic method usually requires extreme reaction conditions such as high temperature and high pressure, with huge energy consumption, extremely high requirements for equipment, and difficult control of the reaction process.

[0004] With the rapid development of modern technology, the medical field has higher and higher requirements for the accuracy of targeted therapy technology, hoping to achieve the targeted effect of active oxygen on specific diseased cells or tissues, minimizing damage to normal tissues while killing pathogens; the biological field pursues more precise regulation means to accurately control the generation and action process of active oxygen in organisms and explore its potential applications in physiological processes such as biological metabolism and signal transduction; the chemical field is committed to developing an innovative system of multiple chemical reactions in synergy, achieving high-selectivity and high-yield generation of active oxygen through the efficient coupling of multi-step reactions. Therefore, it is urgent to develop a method for generating active oxygen that integrates high efficiency, environmental protection and precision and can meet the complex requirements of multiple fields. Summary of the Invention

[0005] Aiming at the above existing technical problems, the primary object of the present invention is to provide a method for electrocatalytically exciting an active oxygen molecular flow from an air source. Compared with traditional electrocatalytic methods, the active oxygen generation rate of the method provided by the present invention is increased by more than 80%, significantly enhancing the production efficiency, greatly reducing the consumption and emission of chemical reagents, and reducing the negative impact on the environment.

[0006] To achieve the above object, the present invention is realized through the following technical solutions:

[0007] The present invention claims protection for a method for electrocatalytically exciting an active oxygen molecular flow from an air source, comprising the following steps:

[0008] S1. The filtered air is ultrasonically oscillated so that the air is dispersed and reorganized, and then the relative humidity of the air is adjusted; or the relative humidity of the filtered air is adjusted, and then the air is ultrasonically oscillated so that the air is dispersed and reorganized;

[0009] S2. The air processed in step S1 is subjected to an electrocatalytic reaction to generate an active oxygen molecular flow;

[0010] The conditions for the electrocatalytic reaction are as follows:

[0011] (1) The anode is a carbon electrode made of carbon nanotubes doped with silver and ruthenium, and the anode has a double helix structure; the cathode uses nickel foam - porous graphene as a carrier, and a nickel - cobalt alloy is loaded on the carrier; the electrolyte used in the electrocatalytic reaction includes amino acids and soluble metal salts;

[0012] (2) A pulsed voltage is applied to the electrocatalytic reaction, and the current density of the electrocatalytic reaction is ≥6 mA / cm 2 .

[0013] In the present invention, the air is subjected to filtration, ultrasonic oscillation and humidity adjustment treatments, which play a synergistic role with the electrode structure, electrolyte formulation and electrocatalytic reaction conditions during subsequent electrolytic catalysis, and have a crucial impact on the generation of active oxygen.

[0014] Specifically, the present invention first filters the air, which can accurately filter out fine particles and microorganisms in the air. This not only provides a pure air environment for subsequent reactions, avoiding interference of impurities with the electrocatalytic reaction (such as preventing impurities from adhering to the electrode surface and affecting electron transfer, and avoiding changing the composition of the electrolyte solution), but also improves the stability of the reaction system, and is an important basis for realizing efficient and stable generation of active oxygen molecular flow.

[0015] Furthermore, the present invention uses ultrasonic oscillation to disperse and reorganize air molecules, greatly improving the activity of the air. When highly active air molecules enter the electrocatalytic reaction, they can participate in the reaction on the electrode surface more quickly and fully, reduce the activation energy of the reaction, accelerate the reaction process, and significantly increase the generation rate of active oxygen.

[0016] Furthermore, adjusting the relative humidity of the air in the present invention can improve the performance of the electrolyte solution during subsequent electrocatalysis, ensuring good electrical conductivity and ion transport ability, thereby promoting the efficient transfer of electrons between the electrode and the electrolyte and providing a favorable reaction environment for the generation of reactive oxygen species. At the same time, appropriate humidity conditions also help to maintain the stability of the electrode material performance, avoiding electrode corrosion or reduced activity caused by abnormal humidity, ensuring the stability and continuity of the reaction process, and thus guaranteeing the continuous generation of reactive oxygen species.

[0017] Furthermore, the air treated in step S1 is subjected to electrocatalysis to obtain reactive oxygen molecules. In the present invention, the anode adopts a unique double-helix structure, which can increase the electrode specific surface area and catalytic active sites. The anode uses doped silver and ruthenium porous graphene, and the cathode is based on nickel foam-porous graphene and loaded with nickel-cobalt alloy, jointly improving the catalytic performance and electron conduction ability of the electrode. The application of pulsed voltage can stimulate different reaction processes at different voltage stages, improving the generation efficiency of reactive oxygen species. A specific current density ensures the efficient and stable progress of the reaction. The amino acids and metal salts in the electrolyte solution cooperate with each other, effectively promoting electron transfer and providing a favorable reaction environment for the generation of reactive oxygen molecules.

[0018] In the present invention, after the air is filtered, ultrasonically oscillated and humidity-adjusted, combined with a specific electrode structure, reaction conditions, etc., the generation rate of reactive oxygen species can be increased by more than 80% compared with the traditional electrocatalysis method. Each link of the air treatment method acts synergistically to provide a pure and appropriately active air raw material for the subsequent electrocatalytic reaction. The double-helix electrode structure and electrocatalytic reaction conditions make the reaction process stable and can continuously generate a reactive oxygen molecule flow for a long time. Using air as the main raw material and the electrolyte solution can be recycled, greatly reducing the consumption and emission of chemical reagents, and having significant environmental protection advantages.

[0019] The reactive oxygen molecule flow prepared by the above method of the present invention can be applied in the fields of environmental protection, medicine, material treatment, etc. In the field of environmental protection, it can be used to decompose various pollutants and purify air and water bodies; in the medical field, it can achieve efficient disinfection and sterilization; in the field of material treatment, it helps with material surface modification, etc.

[0020] Preferably, in step S1, the relative humidity of the filtered air is adjusted, and then ultrasonic oscillation is used to disperse and reorganize the air. Ultrasonic waves can produce cavitation in liquids, thereby generating local high temperatures and then increasing their activity. The inventor found that the effect of ultrasonic cavitation in liquids is better than that in gases. Therefore, adjusting the relative humidity of the filtered air first makes the air more inclined to a liquid environment, which is more conducive to the generation of reactive oxygen molecule flow.

[0021] Preferably, in the step S1, the air is filtered by a nano-net with a pore size of 100-1000 nm. Under this preferred pore size, on the one hand, it can avoid the blockage of aerosols or organic substances, resulting in frequent maintenance or replacement of the filter screen and increasing the operating cost, and can reduce the resistance when the air passes through the nano-net, reducing energy consumption and system energy efficiency; on the other hand, it can avoid intercepting oxygen molecules in the air (the kinetic diameter of oxygen molecules is about 0.346 nm), reducing the oxygen concentration in the air.

[0022] Preferably, in the step S1, the treatment conditions of ultrasonic oscillation are: intermittent pulse mode, 20-50 kHz, 50-300 W.

[0023] Preferably, in the step S1, the time of ultrasonic oscillation is 5-30 min.

[0024] Preferably, in the step S1, the relative humidity of the air is adjusted to 40%-60%. Adjusting the relative humidity of the air to 40%-60% can further enhance the continuous generation of reactive oxygen species. More specifically, the relative humidity of the air can be 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, etc., or the interval range formed by any of the above values, such as 40%-50%, 45%-55%, etc., and the present invention is not limited thereto.

[0025] Preferably, in the step S2, the carbon nanotubes are doped with 0.3-0.7 wt% silver and 0.2-0.5 wt% ruthenium. Further preferably, it is doped with 0.4-0.6 wt% silver and 0.2-0.4 wt% ruthenium. Most preferably, it is doped with 0.5 wt% silver and 0.3 wt% ruthenium. Preferably, the mass ratio of silver to ruthenium is 1-2:1.

[0026] Preferably, the anode is a carbon electrode made by compounding and pressing doped carbon nanotubes with silver and ruthenium with a binder. Further preferably, the mass ratio of carbon nanotubes to the binder is 5-8:3. Preferably, the binder can be the binder conventionally used in the field for preparing electrodes, including but not limited to polytetrafluoroethylene, etc.

[0027] Specifically, in some embodiments, the carbon nanotubes doped with silver and ruthenium can be obtained by purchasing commercially, or can be obtained by conventional methods in the art such as electroless plating.

[0028] More specifically, in some embodiments, the preparation method of the carbon nanotubes doped with silver and ruthenium is as follows: the carbon nanotubes are subjected to electroless plating treatment, and the product is mixed with a binder and then pressed to form a double helix structure and insulated.

[0029] Preferably, the electroless plating treatment includes pretreatment, electroless plating and post-treatment.

[0030] Preferably, the pretreatment includes ultrasonic cleaning, acid oxidation treatment, and sensitization and activation steps.

[0031] More specifically, the double - helix structure includes a first helical electrode and a second helical electrode. The first helical electrode is coaxially arranged from top to bottom and spaced from each other. The first helical electrode and the second helical electrode can be arranged at equal intervals or non - equal intervals. Those skilled in the art can set the spacing distance between the first helical electrode and the second helical electrode according to requirements. More specifically, the spacing distance between the first helical electrode and the second helical electrode is 0.1 - 2 cm.

[0032] Specifically, in some embodiments, the cathode can be obtained by purchasing commercially, or can be prepared by conventional methods in the art such as chemical deposition.

[0033] More specifically, in some embodiments, a method for preparing a nickel - cobalt alloy supported on a nickel foam - porous graphene carrier is as follows:

[0034] (1) Graphene composite: Graphene oxide is ultrasonically dispersed, and then mixed and impregnated with nickel foam and a reducing agent, and calcined to form a substrate;

[0035] (2) The nickel - cobalt alloy is deposited on the substrate by electrodeposition to prepare the cathode.

[0036] Preferably, in the step (1), the reducing agent is ascorbic acid.

[0037] Preferably, in the step (1), the mass ratio of nickel foam to graphene oxide is 3 - 5:1.

[0038] Preferably, in the step (1), the calcination temperature is 280 - 320 °C.

[0039] Preferably, in the step S2, the mass ratio of porous graphene to nickel - cobalt alloy is 1 - 4:1. Further preferably, the mass ratio of porous graphene to nickel - cobalt alloy is 2 - 3:2. Most preferably, the mass ratio of porous graphene to nickel - cobalt alloy is 3:2. Preferably, the ratio of nickel to cobalt in the nickel - cobalt alloy is 1:2 - 5.

[0040] Preferably, in the step S2, the amino acid is selected from one or more of glycine, alanine, and glutamic acid.

[0041] Preferably, in the step S2, the cation of the soluble metal salt is selected from one or more of zinc, copper, iron, and nickel.

[0042] Preferably, in the step S2, the mass ratio of the amino acid to the soluble metal salt is 1-5:1. Further preferably, the mass ratio of the amino acid to the soluble metal salt is 1-2:1.

[0043] Preferably, in the step S2, the current density of the electrocatalytic reaction is 2-14 mA / cm 2 . More specifically, the current density can be 2 mA / cm 2 , 4 mA / cm 2 , 6 mA / cm 2 , 8 mA / cm 2 , 10 mA / cm 2 , 12 mA / cm 2 , 14 mA / cm 2 etc., or the interval range formed by any of the above values, such as 2-12 mA / cm 2 , 4-14 mA / cm 2 , 2-14 mA / cm 2 etc., and the present invention is not limited thereto.

[0044] Preferably, in the step S2, the specific conditions of the pulsed voltage are: the initial voltage is 1.0 V, and it varies periodically between 0.5-3.0 V with an amplitude of 0.1 V, and the frequency is 3-10 Hz.

[0045] Preferably, in the step S2, the reaction temperature of the electrocatalytic reaction is 28-32 °C.

[0046] More specifically, in the step S2, the amplitude of the voltage is controlled to be 1.0-2.5 V. More specifically, the amplitude can be 1.0-2.0 V, 0.5-2.5 V, 1.0-3.0 V, etc., or any acceptable interval, and the present invention is not limited thereto.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] (1) The present invention provides a method for electrocatalytically exciting an active oxygen molecule flow from an air source. The active oxygen molecule flow is prepared by electrocatalytic reaction of air. It uses air as the main raw material, and the electrolyte solution can be recycled, greatly reducing the consumption and emission of chemical reagents, reducing the negative impact on the environment, and conforming to the concepts of green chemistry and sustainable development.

[0049] (2) In the present invention, the air is treated by filtration, ultrasonic oscillation and humidity adjustment, and combined with a specific electrode structure, reaction conditions, etc., the generation rate of active oxygen can be increased by more than 80% compared with the traditional electrocatalytic method. Specific Embodiments

[0050] The present invention will be further described below in conjunction with the specification and specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field.

[0051] The preparation process of the anode of the electrocatalytic reaction device in the embodiment of the present invention is as follows:

[0052] (1) Metal doping: Silver / ruthenium nanoparticles are loaded on the surface of carbon nanotube powder by electroless plating to form a carbon nanocomposite powder doped with silver and ruthenium.

[0053] The electroless plating method includes three steps: pretreatment, electroless plating, and post-treatment.

[0054] The pretreatment process includes three main links: ultrasonic cleaning, acid oxidation treatment, and sensitization and activation. In the ultrasonic cleaning stage, using carbon nanotube powder as the substrate (source: Liquan Technology, highly dispersed carbon nanotube powder (LQ302), particle size ≤ 50nm, specific surface area ≥ 200m 2 / g), placing it in acetone, ultrasonicating for 15 min at 40 kHz, 150 W, and 25 °C, and then ultrasonic cleaning with deionized water 3 times, 15 min each time. Its function is to remove organic pollutants and oxide layers on the surface of the carbon nanotube powder.

[0055] During acid oxidation treatment, first place the material in a solution with a volume ratio of HNO3 (volume concentration of 65%) to deionized water of 1:5 and ultrasonicate for 10 min, then place it in a solution with a volume ratio of HCl (mass fraction of 37%) to deionized water of 1:5 and ultrasonically activate for 5 min, then ultrasonically clean with deionized water 3 times, 15 min each time, and finally dry with nitrogen.

[0056] In the sensitization and activation link, first immerse the material in a sensitizing solution composed of SnCl2·2H2O and HCl (volume ratio of 1:1) with a SnCl2 concentration of 20 g / L and treat it at room temperature for 10 min; then place it in an activating solution composed of PdCl2 and NH4OH (volume ratio of 1:5) with a PdCl2 concentration of 0.5 g / L and treat it at room temperature for 5 min; finally, perform a reduction treatment at room temperature in a 0.1 mol / L NaBH4 solution with pH = 10 for 5 min.

[0057] Electroless plating solution formulation (concentration when using 1 kg of powder as the carrier, 1 kg of powder / 1 L of plating solution)

[0058] Component Concentration (mol / L) Mass (g / L) <![CDATA[AgNO3]]> 0.0463 7.86 <![CDATA[RuCl3·H2O]]> 0.0297 6.92 Sodium citrate 0.6 73.2 Formaldehyde (37%) 0.08 29.9 Thiourea 0.0005 0.05 <![CDATA[NH3·H2O]]> Adjust to pH = 8.8 —— Deionized water Make up to 1 L ——

[0059] Electroless plating process parameters

[0060]

[0061]

[0062] Electroless plating process: First, pour the prepared electroless plating solution into a reaction vessel and preheat it in a constant temperature device (water bath) at 50 ± 1 °C. After the temperature of the electroless plating solution stabilizes, carefully place the pretreated carbon nanotubes into the electroless plating solution to ensure that they are completely immersed and evenly distributed. Then, turn on the magnetic stirrer and stir the plating solution at a speed of 300 rpm to make the components such as silver ions, ruthenium ions, complexing agents, and reducing agents in the electroless plating solution evenly distributed. Under the conditions of 50 °C and a pH of 8.8, the metal ions in the electroless plating solution undergo a reduction reaction and deposition on the surface of the carbon nanotubes under the action of the reducing agent. The plating time is 60 min. During this period, observe the reaction of the plating solution and the change of the coating on the surface of the carbon nanotubes every 15 min, and judge the plating progress and effect by detecting the coating thickness through staged sampling (SEM). At the same time, use a pH meter to monitor the pH value of the plating solution in real time. If there is a fluctuation, adjust it with an alkaline reagent in time to ensure that the pH is stable at 8.8 until the plating is completed. Finally, carbon nanotubes doped with 0.5 wt% silver and 0.3 wt% ruthenium are prepared (hereinafter referred to as "LQ302 / Ag / Ru composite powder", and the doping amounts of silver and ruthenium are based on the mass of the carbon nanotubes).

[0063] Post-treatment: First, perform cleaning. Ultrasonically clean the plated product with deionized water for 10 min and then with ethanol for 5 min; then perform a drying treatment. Put the cleaned product into a vacuum drying oven and anneal it at 300 °C for 30 min.

[0064] (2) Current collector encapsulation: Mix the LQ302 / Ag / Ru composite powder and the binder polytetrafluoroethylene in a mass ratio of 7:3, and press it according to the patent publication number CN107151804A to form a double-helix structure composed of a first helical electrode and a second helical electrode (the first helical electrode and the second helical electrode are coaxially arranged up and down and spaced apart from each other, the tops of the first helical electrode and the second helical electrode are connected, and the spacing distance between the first helical electrode and the second helical electrode is 0.5 cm). Finally, use a silicone rubber insulating layer to isolate the anode and the cathode.

[0065] The preparation process of the cathode of the electrocatalytic reaction device in the embodiment of the present invention is as follows:

[0066] (1) Graphene Composite: Dissolve 1 g of graphene oxide powder (source: Zhongke Times Nano, G-Nano 5080) in 1 L of ethanol. Ultrasonically disperse it under the conditions of 40 kHz and 150 W for 30 minutes. After cooling, centrifuge at 8000 rpm for 5 minutes to remove undispersed particles. Then prepare a 3% (w / v) ascorbic acid ethanol solution as a reducing agent, that is, dissolve 3 g of ascorbic acid in 100 mL of ethanol. Then, immerse nickel foam (the mass ratio of nickel foam to graphene oxide is 4:1) in the mixed solution of graphene oxide and ascorbic acid reducing agent (volume ratio is 1:8), and stir at room temperature for 30 minutes for impregnation. After impregnation, put it into a sintering furnace, and sinter at a temperature of 300 °C for 2 hours under the protection of nitrogen (to prevent oxidation). Finally, perform post-treatment, ultrasonically clean 3 times with deionized water to remove the residual reducing agent, and then dry in a vacuum environment at 60 °C for 24 hours to form a porous graphene substrate.

[0067] (2) Nickel-Cobalt Alloy Deposition: Weigh the mass of the porous graphene substrate, and take nickel-cobalt alloy powder (source: Jinchuan Group, Ni-30% Co alloy, the mass ratio of the porous graphene substrate to the nickel-cobalt alloy is 3:2, the alloy block is made into powder by ball milling method, the ball-to-material ratio of "WC ball" is 15:1, the rotation speed is 250 rpm, and it is milled for 24 h under the protection of argon). Use the electroplating method to electroplate nickel-cobalt alloy powder on the porous graphene substrate at a current density of 5 mA / cm 2 for 30 minutes.

[0068] Example 1

[0069] (1) Air Source Pretreatment: Pass air through a nanofiber filter screen with a pore size of 150 nm through a pipeline; after filtering to remove impurities, it enters the ultrasonic oscillation chamber through a pipeline. In the ultrasonic oscillation chamber, the air is dispersed and reorganized to enhance its activity. The treatment conditions of ultrasonic oscillation are: intermittent pulse mode, 40 kHz, 50 W, 5 - 10 min; then it is transported to the humidity intelligent regulation chamber through a pipeline, and the relative humidity of the air is adjusted to 50%. The air with adjusted humidity finally enters the electrocatalytic reaction device through a pipeline for reaction.

[0070] (2) Install the electrocatalytic reaction device, with the anode and cathode being the anode and cathode prepared above respectively; the concentration of glutamic acid in the electrolyte solution is 0.05 mol / L, the concentration of copper chloride is 0.02 mol / L, and the concentration of zinc sulfate is 0.01 mol / L. Conduct electrocatalytic reaction under the following electrocatalytic reaction conditions to generate an active oxygen molecular flow: Apply a pulsed voltage, the initial voltage is 1.5 V, and it varies between 1.0 - 2.0 V with an amplitude of 0.5 V, the frequency is 5 Hz, the current density is 8 mA / cm 2 , and the temperature is 30 °C.

[0071] Example 2

[0072] The difference between this example and Example 1 is that in step (2), the voltage amplitude is 0.5 - 2.5V.

[0073] Example 3

[0074] The difference between this example and Example 1 is that in step (2), the voltage amplitude is 1.0 - 2.5V.

[0075] Example 4

[0076] The difference between this example and Example 1 is that in step (2), the voltage amplitude is 1.0 - 3.0V.

[0077] Example 5

[0078] The difference between this example and Example 1 is that in step (2), the current density is 6mA / cm 2 .

[0079] Example 6

[0080] The difference between this example and Example 1 is that in step (2), the current density is 10mA / cm 2 .

[0081] Example 7

[0082] The difference between this example and Example 1 is that in step (2), the current density is 12mA / cm 2 .

[0083] Example 8

[0084] The difference between this example and Example 1 is that in step (2), the current density is 14mA / cm 2 .

[0085] Comparative Example 1

[0086] The difference between this comparative example and Example 1 is that in step (1), a nanofiber filter screen was not used for filtration.

[0087] Comparative Example 2

[0088] The difference between this comparative example and Example 1 is that in step (1), an ultrasonic oscillation chamber was not used for oscillation.

[0089] Comparative Example 3

[0090] The difference between this comparative example and Example 1 is that in step (1), a humidity regulator was not used to adjust the relative humidity of the air.

[0091] Comparative Example 4

[0092] The difference between this comparative example and Example 1 is that in step (2), a traditional flat electrode is used.

[0093] Comparative Example 5

[0094] The difference between this comparative example and Example 1 is that in step (2), a constant voltage of 1.5 V is used, and the current density and reaction temperature are the same as those in Example 1.

[0095] Comparative Example 6

[0096] The difference between this comparative example and Example 1 is that in step (2), a conventional electrolyte solution: sulfuric acid with a volume concentration of 50% is used.

[0097] Comparative Example 7

[0098] The difference between this comparative example and Example 1 is that in step (2), carbon nanotubes without doped silver and ruthenium are used as the anode, and a common graphite electrode is used as the cathode.

[0099] Comparative Example 8

[0100] The difference between this comparative example and Example 1 is that in step (2), the current density is 2 mA / cm 2 .

[0101] Comparative Example 9

[0102] The difference between this comparative example and Example 1 is that in step (2), the current density is 4 mA / cm 2 .

[0103] Test Example

[0104] Preparation: Select a quartz tube with an inner diameter of 8 mm, and respectively install the core components of the electrocatalytic reaction device prepared in the examples and comparative examples (including the electrode and the reaction tank filled with the electrolyte solution) into it. The remaining space in the tube is evenly filled with quartz sand to ensure the stability of the reaction system. Place the assembled quartz tube in a special reaction furnace, and connect the gas delivery pipeline and related detection equipment.

[0105] Gas flow control: Precisely control the air flow rate to be 150 mL / min and make it stably enter the reaction system.

[0106] Detection condition setting: Use professional reactive oxygen detection equipment, such as an electron spin resonance spectrometer (ESR) in combination with a suitable scavenger, to detect the hydroxyl radical (·OH) and superoxide anion radical (O2 -·) generation. In this detection, an EMXplus series electron spin resonance spectrometer produced by Bruker of Germany was selected. This device features high sensitivity and high resolution, and can accurately detect the signals of reactive oxygen free radicals.

[0107] Scavenger selection: For hydroxyl radicals (·OH), 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) was used as the scavenger. The reaction between DMPO and ·OH can form a stable spin adduct, generating characteristic peaks on the ESR spectrum, which is convenient for detection and analysis. For superoxide anion radicals (O2 - ·), 2-methyl-2-nitropropane (MNP) was selected as the scavenger. MNP can specifically bind to O2 - ·, presenting unique signal peaks in ESR detection, thereby achieving qualitative and quantitative analysis of superoxide anion radicals.

[0108] Operation steps: Before detection, an appropriate amount of scavenger was added to the reaction system (i.e., the electrolyte solution) to ensure sufficient contact and reaction between the scavenger and reactive oxygen free radicals. Then, the electrolyte solution was placed in the detection cavity of the EMXplus electron spin resonance spectrometer. The instrument parameters were set as follows: the scanning range was 320 - 360 mT, the scanning time was 60 s, the modulation amplitude was 1.0 G, and the microwave power was 20 mW. The instrument was started for real-time detection, and the ESR spectrum of the spin adduct formed by reactive oxygen free radicals and the scavenger was recorded. According to the intensity and number of characteristic peaks in the spectrum, combined with the standard curve, the concentrations of hydroxyl radicals (·OH) and superoxide anion radicals (O2 - ·) were calculated.

[0109] Reaction condition setting and testing: According to the electrocatalytic reaction conditions of each example, the reaction was continued for 60 min. The concentration data of reactive oxygen molecules were recorded every 10 min to evaluate the generation rate and stability of reactive oxygen. The concentrations of hydroxyl radicals and superoxide anion radicals in each example and comparative example were recorded. The test results are shown in Tables 1 and 2 below.

[0110] Table 1

[0111]

[0112]

[0113] Table 2

[0114]

[0115]

[0116] As can be seen from Table 1 and Table 2 above, the reaction process of the method for electrocatalytically exciting and generating reactive oxygen molecule flow provided by the present invention is stable, and can continuously and stably generate reactive oxygen molecule flow for a long time, and can significantly improve the reactive oxygen molecule flow. Further, as can be seen from Table 2 above, within 60 minutes of the method provided by the present invention, the concentration of hydroxyl radicals generated is ≥4.0×10 -5 mol / L, and the concentration of superoxide anion radicals is ≥2.8×10 -5 mol / L.

[0117] As can be seen from Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3, when the nanofiber filter screen is not used for filtration, or ultrasonic oscillation is not used, or the humidity of the air is not adjusted, it is difficult to achieve the technical effects of the present invention.

[0118] As can be seen from Comparative Example 4, Comparative Example 7 and Example 1, using a double-helical structure for the anode can increase the electrode specific surface area and catalytic active sites, thereby improving the generation of reactive oxygen. Using carbon nanotubes doped with silver and ruthenium for the anode and porous graphene loaded with nickel-cobalt alloy for the cathode can significantly improve the generation of reactive oxygen.

[0119] As can be seen from Comparative Example 5 and Example 1, using a pulsed voltage for the electrocatalytic reaction can stimulate different reaction processes at different voltage stages and improve the generation efficiency of reactive oxygen.

[0120] As can be seen from Comparative Example 6 and Example 1, using a combination of amino acids and metal salts as the electrolyte solution of the system can effectively promote electron transfer and provide a favorable reaction environment for the generation of reactive oxygen molecules.

[0121] As can be seen from Comparative Example 8, Comparative Example 9 and Example 1, a specific current density ensures the efficient and stable progress of the reaction.

[0122] The foregoing examples are merely illustrative and are used to explain some features of the method described in the present invention. The appended claims are intended to claim the broadest scope conceivable, and the examples presented herein are supported by the applicant's actual test results. Therefore, the applicant's intention is that the appended claims are not limited by the selection of examples that illustrate the features of the present invention. Some numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be construed as being covered by the appended claims whenever possible.

Claims

1. A method for generating a flow of active oxygen molecules by electrocatalytic excitation of an air source, characterized in that: The steps include: S1. The filtered air is shaken by ultrasonic waves so that the air is broken up and reorganized, and then the relative humidity of the air is adjusted; or the relative humidity of the filtered air is adjusted, and then ultrasonic waves are shaken so that the air is broken up and reorganized; S2. The air treated in step S1 undergoes an electrocatalytic reaction to generate a flow of active oxygen molecules; The conditions of the electrocatalytic reaction are: (1) The anode is a carbon electrode made of carbon nanotubes doped with silver and ruthenium, and the anode has a double helix structure; the cathode uses foam nickel-porous graphene as a carrier, and the carrier is loaded with a nickel-cobalt alloy; the electrolyte used in the electrocatalytic reaction includes amino acids and soluble metal salts; (2) Pulse voltage is applied to the electrocatalytic reaction, and the current density of the electrocatalytic reaction is ≥6mA / cm 2 .

2. The method according to claim 1, characterized in that: In the step S1, the air is filtered using a nanonet with a pore size of 100-1000 nm.

3. The method according to claim 1, characterized in that: In the step S1, the processing conditions of ultrasonic oscillation are: intermittent pulse mode, 20-50kHz, 50-300W.

4. The method according to claim 1, characterized in that: In step S1, the air is conditioned to have a relative humidity of 40%-60%.

5. The method according to claim 1, characterized in that: In the step S2, the carbon nanotubes are doped with 0.3-0.7 wt% silver and 0.2-0.5 wt% ruthenium.

6. The method according to claim 1, characterized in that: In the step S2, the mass ratio of the porous graphene to the nickel-cobalt alloy is 1-4:

1.

7. The method according to claim 1, characterized in that: In step S2, the amino acid is selected from at least one of glycine, alanine and glutamic acid.

8. The method according to claim 1 or 7, characterized in that: In step S2, the cation of the soluble metal salt is selected from one or more of zinc, copper, iron and nickel.

9. The method according to claim 1, characterized in that: In step S2, the molar ratio of the amino acid to the soluble metal salt is 1-5:

1.

10. The method according to claim 1, characterized in that: In step S2, the specific conditions of the pulse voltage are: the initial voltage is 1.0V, the voltage changes periodically between 0.5 and 3.0V with an amplitude of 0.1V, and the frequency is 3-10Hz.

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