Galvanic cell base material capable of directionally generating free radicals, material and preparation method

Abstract

The invention discloses a primary battery base material capable of directionally generating free radicals, a material and a preparation method, and solves the problems that the free radicals generated by a water treatment material are single in type and uncontrollable, and the pertinence on the characteristics of organic pollutants and the degradation of the free radicals and organic matter functional structures is not strong. According to the primary battery base material capable of directionally generating the free radicals, the concentration of the generated free radicals is greatly improved, and the wastewater treatment efficiency is improved; according to the primary battery material capable of directionally generating the free radicals, the primary battery base material capable of directionally generating the free radicals and one of copper, manganese and lanthanum are used as components to synthesize the primary battery material capable of efficiently and directionally generating the free radicals, and the iron-carbon-copper nanometer material can improve generation of superoxide free radicals; the iron-carbon-manganese nano material can improve generation of hydroxyl free radicals, the iron-carbon-lanthanum material can accelerate the generation rate of the free radicals, regulation and control of the generation types of the free radicals are achieved by compounding different metal materials, and the free radicals can also be generated under neutral and alkaline conditions.

Description

Technical Field

[0001] The present invention relates to a primary battery substrate and a preparation method thereof, and in particular to a primary battery substrate, a material and a preparation method thereof that can directionally generate free radicals. Background Art

[0002] Among the many wastewater treatment materials, iron-carbon galvanic cell materials, as a new type of water treatment material, have the advantages of not requiring external energy, low cost, and the ability to simultaneously treat high-concentration organic wastewater and heavy metal pollution. However, when treating wastewater, the iron-carbon galvanic cell reaction is usually controlled under acidic conditions, with a pH value often below 4-6. Under neutral and alkaline conditions, the iron-carbon galvanic cell reaction is slow and easily leads to iron electrode passivation and deactivation, which in turn significantly reduces the concentration of free radicals produced by the iron-carbon galvanic cell. In addition, the free radicals produced by the iron-carbon galvanic cell are of a single type and uncontrollable, and are not very targeted to the characteristics of organic pollutants and their degradation of free radicals and organic functional structures. These current situations limit the use of iron-carbon galvanic cells in actual wastewater treatment.

[0003] In the paper by Xu Ke et al. (see: Research progress on pretreatment of industrial wastewater by iron-carbon micro-electrolysis-Fenton process [J]. Liaoning Chemical Industry, 2022, 51(08): 1134-1136+1169.), it was disclosed that the iron-carbon micro-electrolysis method was combined with the Fenton process to improve the treatment efficiency of industrial wastewater by the iron-carbon micro-electrolysis method, but the additional addition of H2O2 reagent was required, which increased the process cost.

[0004] In Liu Feng's paper (see: Iron-carbon micro-electrolysis technology for pretreatment of cephalosporin synthesis pharmaceutical wastewater [J]. Environmental Impact Assessment, 2017, 39(03): 94-96.), the use of iron-carbon micro-electrolysis to treat pharmaceutical wastewater was disclosed, which achieved relatively good results. However, the pH value of the wastewater needed to be adjusted in advance, which increased the cost of the process.

[0005] A Chinese invention patent with publication number CN112960726B discloses an iron-carbon composite material prepared by a carbon thermal reduction method, which can efficiently remove heavy metal pollutants from water and improve the treatment rate. However, there are high energy consumption caused by the high-temperature process, material structural defects and interface problems. Summary of the Invention

[0006] The purpose of the present invention is to solve the problem that the free radicals generated by water treatment materials are of a single and uncontrollable type, and are not targeted at the characteristics of organic pollutants and the degradation of free radicals and organic functional structures, and to provide a primary battery substrate, material and preparation method that can generate free radicals in a targeted manner.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A primary cell substrate capable of generating free radicals in a targeted manner, wherein the raw materials are composed of 65-75% electron acceptor and 25-35% electron donor by weight;

[0009] The electron acceptor is micron activated carbon particles with a particle size of 100 μm-300 μm;

[0010] The electron donor is nano-iron particles with a particle size of 20nm-100nm;

[0011] The electron donor is loaded in the gaps of the electron acceptor.

[0012] A method for preparing a primary battery substrate capable of directionally generating free radicals is characterized in that it comprises the following steps:

[0013] Step 1: mixing ferric chloride hexahydrate and micron activated carbon particles at a mass ratio of 1:0.4-0.6, dissolving the mixture in an ethanol aqueous solution, and mechanically stirring to obtain micron activated carbon particles with ferric chloride hexahydrate loaded in their pores;

[0014] Step 2: In an oxygen-free environment, adding a reducing agent to the micron activated carbon particles with ferric chloride hexahydrate loaded in the pores, wherein the mass ratio of the reducing agent to the ferric chloride hexahydrate is 0.7-3.7:1, and magnetically stirring to reduce the ferric chloride hexahydrate to nano-iron particles, thereby obtaining micron activated carbon particles with nano-iron particles loaded in the pores;

[0015] Step 3: In an oxygen-free environment, the micron activated carbon particles with nano-iron particles loaded in the pores are filtered, dried, and naturally cooled in sequence to obtain a primary battery substrate that can directionally generate free radicals.

[0016] Furthermore, step 1 is specifically as follows:

[0017] Step 1.1, mixing ethanol and water in a volume ratio of 3:6.5-7.5 to obtain an ethanol-water solution;

[0018] Step 1.2, ferric chloride hexahydrate and micron activated carbon particles are mixed in a mass ratio of 1:0.4-0.6, and dissolved in an ethanol aqueous solution, wherein the mass ratio of the mixed particles to the ethanol aqueous solution is 1:50-80, and mechanical stirring is performed at a stirring speed of 90r / min-120r / min and a stirring time of 22h-24h to obtain micron activated carbon particles with ferric chloride hexahydrate loaded in the pores.

[0019] Furthermore, in step 2:

[0020] The oxygen-free environment is a nitrogen atmosphere;

[0021] The magnetic stirring speed is 300r / min-400r / min, and the stirring time is 20min-30min;

[0022] The reducing agent is sodium borohydride.

[0023] Furthermore, step 3 is specifically as follows:

[0024] In a vacuum filtration device, the micron activated carbon particles loaded with nano-iron particles in the pores are filtered and placed in a vacuum drying oven for drying at a temperature of 55°C to 60°C for 8 hours to 10 hours. The particles are then naturally cooled to room temperature to obtain a primary battery substrate capable of directionally generating free radicals.

[0025] A primary battery material capable of generating free radicals in a directed manner, which is special in that it is composed of the primary battery substrate capable of generating free radicals in a directed manner and metal nanoparticles;

[0026] The mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 90%-99%, and the remainder is metal nanoparticles;

[0027] The metal nanoparticles are one of nano-copper particles, nano-manganese particles, and nano-lanthanum particles;

[0028] The particle size of the metal nanoparticles is 20nm-100nm.

[0029] A method for preparing a primary battery material capable of directionally generating free radicals is characterized in that it comprises the following steps:

[0030] Step 1: mixing the aforementioned galvanic cell substrate capable of generating free radicals in a directed manner with a metal salt at a mass ratio of 25:1-10, dissolving the mixture in an ethanol aqueous solution, and stirring the mixture to obtain a galvanic cell substrate capable of generating free radicals in which the metal salt is loaded in the pores;

[0031] Wherein, the metal salt is one of copper sulfate pentahydrate, manganese chloride, and lanthanum nitrate hexahydrate;

[0032] Step 2: Under anaerobic conditions, a reducing agent is added to the galvanic cell substrate capable of directionally generating free radicals and having metal salts loaded in the pores, wherein the mass ratio of the reducing agent to the metal salt in step 1 is 9-19:1, and magnetic stirring is performed to reduce the metal salt to metal nanoparticles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with metal nanoparticles;

[0033] Step 3: In an oxygen-free environment, the primary battery substrate capable of directionally generating free radicals and loaded with metal nanoparticles is filtered, dried, and naturally cooled in sequence to obtain a primary battery material capable of directionally generating free radicals.

[0034] Furthermore, step 1 is specifically as follows:

[0035] Step 1.1, mixing ethanol and water in a volume ratio of 3:6.5-7.5 to obtain an ethanol-water solution;

[0036] Step 1.2, the above-mentioned primary battery substrate capable of directionally generating free radicals is mixed with a metal salt in a mass ratio of 25:1-10 to obtain a mixed material, the mixed material is dissolved in an ethanol aqueous solution, the mass ratio of the mixed material to the ethanol aqueous solution is 1:100-200, and mechanical stirring is performed at a speed of 90r / min-120r / min and a stirring time of 22h-24h to obtain a primary battery substrate capable of directionally generating free radicals with a metal salt loaded in the pores; the metal salt is one of copper sulfate pentahydrate, manganese chloride, and lanthanum nitrate hexahydrate.

[0037] Furthermore, in step 2:

[0038] The oxygen-free condition is a nitrogen atmosphere;

[0039] The reducing agent is sodium borohydride;

[0040] The rotation speed of the magnetic stirring is 300r / min-400r / min, and the stirring time is 20min-30min.

[0041] Furthermore, step 3 is specifically as follows:

[0042] In a vacuum filtration device, the primary battery substrate capable of directionally generating free radicals loaded with metal nanoparticles is filtered and placed in a vacuum drying oven for drying at a temperature of 55°C to 60°C for 8 hours to 10 hours. The substrate is cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0043] Beneficial effects of the present invention:

[0044] 1. The present invention provides a primary battery substrate capable of directionally generating free radicals and a preparation method. A primary battery substrate capable of directionally generating free radicals is synthesized using nano-iron particles and micron-particle activated carbon as synthetic components. Compared with traditional primary battery materials, this material significantly increases the concentration of free radicals generated, thereby improving wastewater treatment efficiency.

[0045] 2. The present invention provides a primary battery material that can generate free radicals in a directionally controlled manner. First, compared with traditional materials, the use of a primary battery substrate that can generate free radicals in a directionally controlled manner greatly improves the electron transfer efficiency of the material, thereby significantly increasing the reaction rate compared to traditional materials. Second, a metal-selective composite strategy is adopted to introduce copper, manganese, or lanthanum metal nanoparticles. The dense oxide film formed in situ by these metal nanoparticles on the surface of the material can significantly reduce the corrosion rate of the iron electrode, thereby extending the service life of the material.

[0046] 3. The present invention provides a galvanic cell material capable of directional free radical generation. By combining different transition metals (such as copper, manganese, and lanthanum) with iron-carbon materials, the type of free radical generated in the galvanic cell can be regulated. The combination of different metals will produce specific types of free radicals: the copper composite system tends to generate superoxide free radicals. The manganese composite system is conducive to the generation of hydroxyl radicals (·OH). This metal selective regulation mechanism breaks through the limitations of traditional iron-carbon materials in the generation of free radicals. According to actual application requirements, the target free radicals can be obtained by selecting specific metal composites, which significantly improves the applicability and treatment effect of the material under different environmental conditions. If lanthanum (La) elements are introduced, the free radical generation efficiency of the material is significantly improved. The compound of La can accelerate the generation of free radicals through the following mechanisms: (1) La 3+ / La 2+ The redox electron pairs effectively promote the electron transfer process; (2) the La-OH active site significantly reduces the H2O2 decomposition energy barrier; (3) the La-Fe synergistic effect optimizes the interfacial electronic structure. Experiments have confirmed that the free radical generation rate of the La composite material is significantly improved compared to traditional iron-carbon materials.

[0047] 4. The present invention provides a method for preparing a galvanic cell material capable of generating free radicals in a targeted manner. The nanoparticle-sized water treatment material is prepared by a liquid phase reduction method. By precisely controlling the solution environment, the type of free radicals generated during the reaction can be selectively controlled. Superoxide radicals can be efficiently generated under neutral alkaline conditions. This controllable free radical generation mechanism enables the material to achieve optimized catalytic performance based on the needs of different application scenarios. DETAILED DESCRIPTION

[0048] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments. Obviously, the embodiments described are only some of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0049] Example 1

[0050] This embodiment provides a primary battery substrate capable of directionally generating free radicals, comprising: 6.5 g of micron activated carbon particles with a particle size of 100 μm-300 μm, and 2.8 g of nano iron particles with a particle size of 20 nm-100 nm; wherein the micron activated carbon particles are electron acceptors, and the nano iron particles are electron donors; the electron donors are loaded in the gaps of the electron acceptors.

[0051] This embodiment provides a method for preparing a primary battery substrate capable of directionally generating free radicals, comprising the following steps:

[0052] Step 1: Mix 600 ml of ethanol and 1400 ml of water to obtain an ethanol-water solution; mix 13 g of ferric chloride hexahydrate and 6.5 g of micron activated carbon particles, and dissolve them in 975 ml of ethanol-water solution. Mechanically stir at a stirring speed of 90 r / min for 24 hours to obtain micron activated carbon particles with ferric chloride hexahydrate loaded in the pores.

[0053] Step 2: In a nitrogen atmosphere, 9.1 g of sodium borohydride was added to 19.5 g of the micron activated carbon particles with ferric chloride hexahydrate loaded in the pores, and the mixture was magnetically stirred at a speed of 300 r / min for 20 min to reduce the ferric chloride hexahydrate to nano-iron particles, thereby obtaining micron activated carbon particles with nano-iron particles loaded in the pores;

[0054] Step 3: In a vacuum filtration device, the micron activated carbon particles loaded with nano-iron particles in the pores are filtered and placed in a vacuum drying oven for drying at a temperature of 60°C for 8 hours. The particles are naturally cooled to room temperature to obtain a primary battery substrate capable of directionally generating free radicals.

[0055] This embodiment also provides a galvanic cell material capable of directionally generating free radicals, which is composed of the above-mentioned galvanic cell substrate capable of directionally generating free radicals and nano-copper particles with a particle size of 20nm-100nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 99%, and the mass percentage of the nano-copper particles is 1%.

[0056] This embodiment provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0057] Step 1: Mix 600 ml of ethanol with 1400 ml of water to obtain an ethanol-water solution; add 0.4 g of copper sulfate pentahydrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1700 ml of ethanol-water solution, mechanically stir at a speed of 90 r / min, and stir for 22 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0058] Step 2: Under a nitrogen atmosphere, 3.6 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles;

[0059] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 55° C. for 8 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0060] The primary battery material capable of directionally generating free radicals obtained in Example 1 was subjected to an in-situ free radical generation performance test at pH = 7.0.

[0061] Example 2

[0062] The difference between this embodiment and embodiment 1 is that:

[0063] This embodiment provides a galvanic cell material capable of directionally generating free radicals, which is composed of the galvanic cell substrate capable of directionally generating free radicals obtained in Example 1 and nano-copper particles with a particle size of 20 nm to 100 nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%, and the mass fraction of the nano-copper particles is 5%.

[0064] This embodiment provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0065] Step 1: Mix 600 ml of ethanol with 1400 ml of water to obtain an ethanol-water solution; add 2 g of copper sulfate pentahydrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1400 ml of the ethanol-water solution, and mechanically stir at a speed of 90 r / min for 22 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0066] Step 2: Under a nitrogen atmosphere, 18 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles;

[0067] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 55° C. for 8 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0068] The primary battery material capable of directionally generating free radicals obtained in Example 2 was subjected to an in-situ free radical generation performance test under the condition of pH=7.0.

[0069] Example 3

[0070] The difference between this embodiment and embodiment 1 is that:

[0071] This embodiment provides a galvanic cell material capable of directionally generating free radicals, which is composed of the galvanic cell substrate capable of directionally generating free radicals obtained in Example 1 and nano-copper particles with a particle size of 20nm-100nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 90%, and the mass percentage of the nano-copper particles is 10%.

[0072] This embodiment also provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0073] Step 1: Mix 600 ml of ethanol with 1400 ml of water to obtain an ethanol-water solution; add 4 g of copper sulfate pentahydrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1600 ml of ethanol-water solution, mechanically stir at a speed of 90 r / min, and stir for 22 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0074] Step 2: Under a nitrogen atmosphere, 36 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles;

[0075] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 55° C. for 8 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0076] The primary battery material capable of directionally generating free radicals obtained in Example 3 was subjected to an in-situ free radical generation performance test under the condition of pH=7.0.

[0077] Example 4

[0078] The difference between this embodiment and embodiment 1 is that:

[0079] This embodiment provides a galvanic cell material capable of directionally generating free radicals, which is composed of the galvanic cell substrate capable of directionally generating free radicals obtained in Example 1 and nano-copper particles with a particle size of 20nm-100nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%, and the mass percentage of the nano-copper particles is 5%.

[0080] This embodiment also provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0081] Step 1: Mix 600 ml of ethanol with 1400 ml of water to obtain an ethanol-water solution; add 2 g of copper sulfate pentahydrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 2000 ml of ethanol-water solution, and mechanically stir at a speed of 90 r / min for 22 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0082] Step 2: Under a nitrogen atmosphere, 18 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles;

[0083] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 55° C. for 8 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0084] The primary battery material capable of directionally generating free radicals obtained in Example 4 was subjected to an in-situ free radical generation performance test under the condition of pH=5.0.

[0085] Example 5

[0086] This embodiment provides a primary battery substrate capable of directionally generating free radicals, comprising: 6.5 g of micron activated carbon particles with a particle size of 100 μm-300 μm, and 2.2 g of nano iron particles with a particle size of 20 nm-100 nm; wherein the micron activated carbon particles are electron acceptors, and the nano iron particles are electron donors; the electron donors are loaded in the gaps of the electron acceptors.

[0087] This embodiment also provides a method for preparing a primary battery substrate capable of directionally generating free radicals, comprising the following steps:

[0088] Step 1: 600 ml of ethanol and 1300 ml of water are mixed to obtain an ethanol-water solution; 11.2 g of ferric chloride hexahydrate is mixed with 6.5 g of micron activated carbon particles and dissolved in 1360 ml of the ethanol-water solution, and mechanically stirred at a stirring speed of 100 r / min for 23 h to obtain micron activated carbon particles with ferric chloride hexahydrate loaded in the pores.

[0089] Step 2: In a nitrogen atmosphere, 33 g of sodium borohydride was added to the micron activated carbon particles with ferric chloride hexahydrate loaded in the pores, and magnetic stirring was performed at a speed of 350 r / min for 25 min to reduce the ferric chloride hexahydrate to nano-iron particles, thereby obtaining micron activated carbon particles with nano-iron particles loaded in the pores;

[0090] Step 3: In a vacuum filtration device, the micron activated carbon particles loaded with nano-iron particles in the pores are filtered and placed in a vacuum drying oven for drying at a temperature of 50°C for 9 hours. The particles are naturally cooled to room temperature to obtain a primary battery substrate capable of directionally generating free radicals.

[0091] This embodiment also provides a galvanic cell material capable of directionally generating free radicals, which is composed of the above-mentioned galvanic cell substrate capable of directionally generating free radicals and nano-copper particles with a particle size of 20nm-100nm; the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%, and the mass percentage of the nano-copper particles is 5%.

[0092] This embodiment also provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0093] Step 1: 600 ml of ethanol and 1400 ml of water are mixed to obtain an ethanol-water solution; 2 g of copper sulfate pentahydrate is added to 10 g of a primary battery substrate capable of directionally generating free radicals and mixed to obtain a mixed material; the mixed material is dissolved in 1200 ml of the ethanol-water solution, and mechanically stirred at a speed of 100 r / min for 23 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0094] Step 2: Under a nitrogen atmosphere, 30 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 350 r / min for 25 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles.

[0095] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 50° C. for 9 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0096] The primary battery material capable of directionally generating free radicals obtained in Example 5 was subjected to an in-situ free radical generation performance test at pH = 7.0.

[0097] Example 6

[0098] This embodiment provides a primary battery substrate capable of directionally generating free radicals, comprising: 6.5 g of micron activated carbon particles with a particle size of 100 μm-300 μm and 3.2 g of nano iron particles with a particle size of 20 nm-100 nm; wherein the micron activated carbon particles are electron acceptors and the nano iron particles are electron donors; the electron donors are loaded in the gaps of the electron acceptors.

[0099] This embodiment provides a method for preparing a primary battery substrate capable of directionally generating free radicals, comprising the following steps:

[0100] Step 1: Mix 600 ml of ethanol and 1500 ml of water to obtain an ethanol-water solution; mix 15.8 g of ferric chloride hexahydrate and 6.5 g of micron activated carbon particles and dissolve them in 1250 ml of ethanol-water solution, mechanically stir at a stirring speed of 120 r / min and a stirring time of 22 h to obtain micron activated carbon particles with ferric chloride hexahydrate loaded in the pores.

[0101] Step 2: In a nitrogen atmosphere, 57 g of sodium borohydride was added to the micron activated carbon particles with ferric chloride hexahydrate loaded in the pores, and magnetic stirring was performed at a speed of 400 r / min for 30 min to reduce the ferric chloride hexahydrate to nano-iron particles, thereby obtaining micron activated carbon particles with nano-iron particles loaded in the pores;

[0102] Step 3: In a vacuum filtration device, the micron activated carbon particles loaded with nano-iron particles in the pores are filtered and placed in a vacuum drying oven for drying at a temperature of 60°C for 8 hours. The particles are naturally cooled to room temperature to obtain a primary battery substrate capable of directionally generating free radicals.

[0103] This embodiment also provides a galvanic cell material capable of directionally generating free radicals, which is composed of the above-mentioned galvanic cell substrate capable of directionally generating free radicals and nano-copper particles with a particle size of 20nm-100nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%, and the mass percentage of the nano-copper particles is 5%.

[0104] This embodiment provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0105] Step 1: Mix 600 ml of ethanol and 1400 ml of water to obtain an ethanol-water solution; add 2 g of copper sulfate pentahydrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1200 ml of the ethanol-water solution, and mechanically stir at a speed of 120 r / min for 24 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0106] Step 2: Under a nitrogen atmosphere, 38 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 400 r / min for 30 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles.

[0107] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 60° C. for 10 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0108] The primary battery material capable of directionally generating free radicals obtained in Example 6 was subjected to an in-situ free radical generation performance test at pH = 7.0.

[0109] Example 7

[0110] The difference between this embodiment and embodiment 1 is that:

[0111] This embodiment provides a galvanic cell material capable of directionally generating free radicals, which is composed of the galvanic cell substrate capable of directionally generating free radicals in Example 1 and nano-copper particles with a particle size of 20nm-100nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%, and the mass percentage of the nano-copper particles is 5%.

[0112] This embodiment provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0113] Step 1: Mix 600 ml of ethanol with 1400 ml of water to obtain an ethanol-water solution; add 2 g of copper sulfate pentahydrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1500 ml of ethanol-water solution, and mechanically stir at a speed of 90 r / min for 22 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0114] Step 2: Under a nitrogen atmosphere, 18 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles;

[0115] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 55° C. for 8 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0116] The primary cell material capable of directionally generating free radicals obtained in Example 7 was tested for its performance of in-situ free radical generation under the condition of pH = 9.0.

[0117] Example 8

[0118] The difference between this embodiment and embodiment 1 is that:

[0119] This embodiment provides a galvanic cell material capable of directionally generating free radicals, which is composed of the galvanic cell substrate capable of directionally generating free radicals prepared in the above embodiment 1 and nano-copper particles with a particle size of 20nm-100nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%, and the mass percentage of the nano-copper particles is 5%.

[0120] This embodiment also provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0121] Step 1: Mix 600 ml of ethanol with 1400 ml of water to obtain an ethanol-water solution; add 2 g of copper sulfate pentahydrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1200 ml of the ethanol-water solution, and mechanically stir at a speed of 90 r / min for 22 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0122] Step 2: Under a nitrogen atmosphere, 18 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles;

[0123] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 55° C. for 8 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0124] The primary battery material capable of directionally generating free radicals obtained in Example 8 was tested for its performance of in-situ free radical generation under the condition of pH=8.0.

[0125] Example 9

[0126] The difference between this embodiment and embodiment 1 is that:

[0127] This embodiment provides a galvanic cell material capable of directionally generating free radicals, which is composed of the galvanic cell substrate capable of directionally generating free radicals obtained in Example 1 and nano-copper particles with a particle size of 20nm-100nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%, and the mass percentage of the nano-copper particles is 5%.

[0128] This embodiment also provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0129] Step 1: Mix 600 ml of ethanol with 1400 ml of water to obtain an ethanol-water solution; add 2 g of copper sulfate pentahydrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1300 ml of ethanol-water solution, and mechanically stir at a speed of 90 r / min for 22 hours to obtain a primary battery substrate capable of directionally generating free radicals with copper sulfate pentahydrate loaded in the pores.

[0130] Step 2: Under a nitrogen atmosphere, 18 g of sodium borohydride was added to the galvanic cell substrate capable of directionally generating free radicals and loaded with copper sulfate pentahydrate in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the copper sulfate pentahydrate to nano-copper particles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with nano-copper particles;

[0131] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-copper particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 55° C. for 8 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0132] The primary battery material capable of directionally generating free radicals obtained in Example 9 was subjected to an in-situ free radical generation performance test at pH=6.0.

[0133] Example 10

[0134] The difference between this embodiment and embodiment 1 is that:

[0135] This embodiment provides a galvanic cell material capable of directionally generating free radicals, which is composed of a galvanic cell substrate capable of directionally generating free radicals obtained in the embodiment and nano-manganese particles with a particle size of 20nm-100nm; wherein the mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%, and the mass percentage of the nano-manganese particles is 5%.

[0136] This embodiment also provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0137] Step 1: Mix 600 ml of ethanol and 1400 ml of water to obtain an ethanol-water solution; add 2 g of manganese chloride to 10 g of a primary cell substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1500 ml of the ethanol-water solution, and mechanically stir at a speed of 90 r / min for 22 hours to obtain a primary cell substrate capable of directionally generating free radicals with manganese chloride loaded in the pores.

[0138] Step 2: Under a nitrogen atmosphere, 18 g of sodium borohydride was added to the galvanic cell substrate capable of directional free radical generation and loaded with manganese chloride in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the manganese chloride to nano-manganese particles, thereby obtaining a galvanic cell substrate capable of directional free radical generation loaded with nano-manganese particles;

[0139] Step 3: In a vacuum filtration device, filter the primary battery substrate that can directionally generate free radicals and is loaded with metal nanoparticles, and place it in a vacuum drying oven for drying at a temperature of 55°C for 8 hours. Cool it to room temperature to obtain a primary battery material that can directionally generate free radicals.

[0140] The primary cell material capable of directionally generating free radicals obtained in this example was subjected to an in-situ free radical generation performance test under the condition of pH=7.0.

[0141] Example 11

[0142] The difference between this embodiment and embodiment 1 is that:

[0143] This embodiment provides a primary battery material capable of directionally generating free radicals, which is composed of the primary battery substrate capable of directionally generating free radicals obtained in Example 1 and nano-lanthanum particles with a particle size of 20nm-100nm; wherein the mass percentage of the primary battery substrate capable of directionally generating free radicals is 95%, and the mass percentage of the nano-lanthanum particles is 5%.

[0144] This embodiment also provides a method for preparing a primary battery material capable of directionally generating free radicals, comprising the following steps:

[0145] Step 1: Mix 600 ml of ethanol with 1400 ml of water to obtain an ethanol-water solution; add 2 g of lanthanum nitrate to 10 g of a primary battery substrate capable of directionally generating free radicals and mix them to obtain a mixed material; dissolve the mixed material in 1500 ml of ethanol-water solution, and mechanically stir at a speed of 90 r / min for 22 hours to obtain a primary battery substrate capable of directionally generating free radicals with lanthanum nitrate loaded in the pores.

[0146] Step 2: Under a nitrogen atmosphere, 18 g of sodium borohydride was added to the galvanic cell substrate capable of directional free radical generation in which lanthanum nitrate was loaded in the pores, and magnetic stirring was performed at a speed of 300 r / min for 20 min to reduce the lanthanum nitrate to nano-lanthanum particles, thereby obtaining a galvanic cell substrate capable of directional free radical generation loaded with nano-lanthanum particles;

[0147] Step 3: In a vacuum filtration device, the primary battery substrate loaded with nano-lanthanum particles capable of directionally generating free radicals is filtered and placed in a vacuum drying oven for drying at a temperature of 55° C. for 8 hours, and then cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

[0148] The primary battery material capable of directionally generating free radicals obtained in Example 11 was subjected to an in-situ free radical generation performance test at pH = 7.0.

[0149] Comparative Example 1

[0150] This comparative example provides a micron primary battery material, including: 6.5g of micron activated carbon particles with a particle size of 100μm-300μm and 2.8g of micron iron powder with a particle size of 0.5μm-10μm; wherein, the micron activated carbon particles are electron acceptors and the micron iron powder is an electron donor; the electron donor is loaded in the gaps of the electron acceptor.

[0151] This comparative example also provides a method for preparing a micron primary battery material, comprising the following steps:

[0152] Step 1: Mix 600 ml of ethanol and 1400 ml of water to obtain an ethanol-water solution; mix 2.8 g of micron iron powder and 6.5 g of micron activated carbon particles, and dissolve them in 975 ml of ethanol-water solution. Mechanically stir at a stirring speed of 90 r / min for 24 hours to obtain micron activated carbon particles with micron iron powder loaded in the pores.

[0153] Step 2: In a vacuum filtration device, the micron activated carbon particles loaded with micron iron powder in the pores are filtered and placed in a vacuum drying oven for drying at a temperature of 60°C for 8 hours. The particles are naturally cooled to room temperature to obtain micron primary battery materials.

[0154] The micronized primary battery material obtained in this comparative example was subjected to an in-situ free radical generation performance test under the condition of pH=7.0.

[0155] The galvanic cell materials capable of directionally generating free radicals of Examples 1-11 and the micron galvanic cell material of Comparative Example 1 were subjected to in-situ free radical generation performance testing of the composite materials. The specific steps are as follows:

[0156] (1) Prepare 200 ml of 100 mg / L coumarin solution and place it in a 250 ml beaker. Add 100 mg of the material to be tested to the coumarin solution. Seal the beaker with sealing film and place it on a magnetic stirrer. React at 200 rpm for 60 min.

[0157] (2) After every 5 min, 10 min, 15 min, 30 min, 45 min, and 60 min, take 3 ml and add it to a quartz cuvette. Use a fluorescence photometer to test the concentration of the product generated by the test material and hydroxyl groups at different times under the conditions of emission wavelength of 453.0 nm, excitation light of 332.0 nm, and emission and excitation slits of 5.0 nm. Calculate the corresponding hydroxyl radical concentration based on the conversion relationship.

[0158] (3) Prepare 200 ml of 1.6 mg / L NBD-Cl (4-chloro-7-nitro-2,1,3-benzoxadiazole) solution and place it in a 250 ml beaker. Add 100 mg of the material to be tested to the NBD-Cl solution. Seal the beaker with sealing film and place it on a magnetic stirrer. React at 200 rpm for 60 min.

[0159] (4) After every 5 min, 10 min, 15 min, 30 min, 45 min, and 60 min, take 3 ml and add it to a quartz cuvette. Use a fluorescence photometer to measure the concentration of the product produced by the test material and superoxide anions at different times under the conditions of an emission wavelength of 550.0 nm, an excitation light of 470.0 nm, and an emission and excitation slit of 5.0 nm. Calculate the corresponding superoxide anion concentration based on the conversion relationship.

[0160] The performance test results are as follows:

[0161] 1. The comparison of the effects of different composite metal contents on the free radical generation of the primary cell substrate capable of efficiently and directionally generating free radicals is shown in Table 1:

[0162] Table 1

[0163]

[0164] As shown in Table 1, in the present invention's galvanic cell material capable of targeted free radical generation, the concentration of hydroxyl radicals first decreases and then increases as the composite copper content increases from 1% to 10%. This is due to the following principle: copper has a higher standard electrode potential than iron. The introduction of copper into an iron-carbon galvanic cell alters the cell's electrode potential distribution. Iron, as the negative electrode, is more likely to lose electrons, which are then transferred to the carbon electrode surface. The presence of copper increases the electron cloud density on the carbon electrode surface, making it easier for oxygen to acquire electrons and generate superoxide anions.

[0165] The concentration of superoxide anion radicals first rises and then falls. The principle is that when copper is present, copper can form a relatively stable complex with superoxide anions, preventing the occurrence of superoxide anion disproportionation reaction, for example:

[0166]

[0167] This reduces the generation of hydrogen peroxide and, in turn, the generation of hydroxyl radicals.

[0168] The results show that the strengthening effect of copper on free radical catalytic nanomaterials is reflected in the generation of superoxide anion radicals, and the strengthening effect is most obvious when the addition amount of the composite metal is 5%.

[0169] 2. The comparison of the effects of different composite metal types on the free radical generation of the primary battery material capable of efficiently and directionally generating free radicals is shown in Table 2:

[0170] Table 2

[0171]

[0172] As shown in Table 2, compared to the micronized primary cell synthesized in Comparative Example 1, the primary cell substrate synthesized in Example 1 generated a 736% increase in hydroxyl radical concentration and a 684% increase in superoxide anion concentration, with both rates of free radical generation increasing by nearly tenfold. This can be explained from the following two aspects:

[0173] First, the specific surface area of ​​nano-scale particles is much larger than that of micron-scale particles. Taking the spherical model as an example, when the particle size is reduced from 1 micron to 10 nanometers, its specific surface area can increase by more than a hundred times, which greatly expands the contact interface between iron and carbon, providing a large number of active sites for the primary cell reaction, greatly promoting the occurrence of electron transfer and chemical reactions.

[0174] Secondly, the unique quantum size effect of nanomaterials plays an important role. This effect changes the electronic structure of nanoscale iron-carbon materials, making their electron migration more efficient, promoting the oxidation process of iron more quickly, and accelerating the Fe 2+ / Fe 3+ The cyclic conversion of carbon atoms and the electron transfer path on the carbon surface are optimized, so that electrons can participate in the free radical generation reaction more smoothly.

[0175] From Examples 2, 10, and 11, it can be seen that different metals combined with free radical catalytic nanomaterials have different catalytic directions. Compounding manganese with free radical catalytic nanomaterials can increase the concentration of hydroxyl radicals generated by the free radical catalytic nanomaterials. The principle is as follows:

[0176] When manganese is present, manganese oxide or manganese ion can act as a catalyst to accelerate the reduction reaction of oxygen on the electrode surface, while affecting the generation and conversion of reaction intermediates. 2+ Can be oxidized to Mn by superoxide anions 3+ , the reaction process is as follows:

[0177]

[0178] Composite copper in free radical catalytic nanomaterials can increase the concentration of superoxide anion radicals produced by the free radical catalytic nanomaterials. In particular, composite copper can significantly increase the concentration of superoxide anion radicals produced by the primary battery material that can generate free radicals in a targeted manner. The principle is as follows:

[0179] When copper is present, it can form a relatively stable complex with superoxide anions, preventing the occurrence of superoxide anion disproportionation reactions, such as:

[0180]

[0181] Wherein, n represents the complexation coefficient.

[0182] This reduces the generation of hydrogen peroxide and, in turn, the generation of hydroxyl radicals.

[0183] When lanthanum is present, the concentrations of hydroxyl radicals and superoxide anion radicals in the system are increased, and the reaction rate is greatly increased. 3+ It can be adsorbed on the electrode surface through electrostatic interaction, changing the charge distribution and electric field strength on the electrode surface, promoting electron transfer and the generation of reaction intermediates. On the other hand, lanthanum compounds have certain catalytic activity, which can accelerate the electronic process of oxygen at the positive electrode and accelerate the decomposition of intermediates such as hydrogen peroxide, thereby generating more hydroxyl radicals faster. The reaction process is as follows:

[0184] Lanthanum can catalyze the positive electrode oxygen to obtain electrons to generate superoxide anions:

[0185]

[0186] Superoxide anions undergo disproportionation to produce hydrogen peroxide:

[0187]

[0188] La 3+ Promote the decomposition of hydrogen peroxide to produce hydroxyl radicals:

[0189]

[0190] 3. The effects of different synthesis conditions on the generation of free radicals by the primary battery material capable of efficiently and directionally generating free radicals are shown in Table 3:

[0191] Table 3

[0192]

[0193]

[0194] According to Table 3, different electron donor contents of the primary battery material that can generate free radicals in a directionally manner will affect the free radical generation performance of the material. Compared with Examples 5 and 6, the electron donor content of the material in Example 2 is moderate. The reason is that when the iron content is too high, insufficient carbon carriers will hinder electron transfer, iron particles are prone to agglomeration and reduce the specific surface area, and the self-corrosion reaction of iron may cause internal circulation of electrons, thereby reducing the electrons involved in free radical generation; when the iron content is too low, iron is insufficient as an electron donor, the number of iron-carbon microbatteries is small, and the adsorption effect of carbon may dominate, all of which limit the continued electron supply and free radical generation reaction.

[0195] In addition, under different stirring and drying time conditions, the material exhibits different free radical generation performance. Compared with Examples 5 and 6, the material in Example 2 has a low stirring speed and a long stirring time during the stirring process, and a long drying time after reduction. Under these conditions, the primary battery material capable of directional free radical generation prepared has the best performance. The reasons are as follows:

[0196] Excessively high stirring speeds can generate significant shear forces on the iron-carbon electrode surface, disrupting the electrode's surface microstructure and active sites. On the one hand, this shear force can cause some active materials on the electrode surface to fall off or become covered, thereby reducing the number of active sites available for free radical generation. On the other hand, altered electrode surface microstructure can affect electron transfer efficiency, hindering the process and hindering free radical generation.

[0197] Furthermore, too short a drying time can lead to insufficient structural stability in the material, resulting in the formation of unstable chemical bonds or lattice defects. These instabilities can affect the distribution of electron clouds and the formation of active sites on the material surface, making the electron transfer process less smooth and hindering the generation of free radicals.

[0198] 4. The effects of different pH values ​​on the generation of hydroxyl radicals by the primary battery material capable of efficiently and directionally generating free radicals are shown in Table 4:

[0199] Table 4

[0200]

[0201] According to Table 4, under different pH conditions, the types of free radicals generated by the primary battery materials that can generate free radicals in a directionally different manner are different.

[0202] Under acidic conditions, the primary battery materials that can generate free radicals in a directional manner tend to produce hydroxyl radicals rather than superoxide anion radicals. The principle is as follows:

[0203] Under acidic conditions, It is protonated and converted into H2O2, which is then catalyzed by Fe / Cu to generate OH (Fenton / Fenton-like reaction). The reaction is as follows:

[0204]

[0205] Fe 2+ +H2O2→Fe 3+ +OH - + OH

[0206] Cu + +H2O2→Cu 2+ +OH - + OH

[0207] In addition, under acidic conditions, a large number of hydrogen ions participate in the reaction, making it easier for oxygen to obtain electrons and be reduced to water, thereby inhibiting the generation of superoxide anions by single-electron reduction of oxygen and inhibiting the O2 reduction path. In an acidic environment, O2 mainly generates water through a four-electron reduction path, reducing The formation of OH makes the reaction path preferentially directed to OH rather than

[0208] Under alkaline conditions, the primary battery materials that can generate free radicals in a directional manner tend to produce superoxide anion radicals rather than hydroxyl radicals. The principle is as follows:

[0209] On the one hand, alkaline environment promotes the single electron reduction of O2 to Carbon materials and Cu + / Cu 2+ Enhance electron transfer, the reaction is as follows:

[0210]

[0211] On the other hand, Fe hydroxide precipitation leads to Fe 2+ 、Fe 3+ The concentration of Fe 2+ When the concentration drops significantly, H2O2 will undergo disproportionation decomposition, further reducing the reaction as follows:

[0212] Fe 2+ +2OH -→Fe(OH)2↓

[0213] Fe 3+ +2OH - →Fe(OH)3↓

[0214] 2H2O2→2H2O+O2↑

[0215] In summary, the present invention adopts a metal selective composite strategy and achieves the inhibition of hydroxyl radicals (·OH) and superoxide radicals by introducing different nano-metal particles such as Cu, Mn, and La. Controllable generation; in addition, the primary battery material that can generate free radicals in a directed manner can optimize the selectivity of free radical products by regulating pH. Under acidic conditions, the concentration of hydroxyl radicals generated by the primary battery material that can generate free radicals in a directed manner increases; under alkaline conditions, the concentration of superoxide anion radicals generated by the primary battery material that can generate free radicals in a directed manner increases.

[0216] The above description is merely a specific embodiment of the present invention, and a comparison of the effects of the specific embodiment with the relevant comparative examples. However, the scope of protection of the present invention is not limited thereto. Any changes or substitutions within the technical scope disclosed in the present invention shall be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be based on the scope of protection of the claims.

Claims

1. A primary cell substrate capable of directionally generating free radicals, characterized in that: The mass percentage composition of each raw material is: electron acceptor 65-75%, electron donor 25%-35%; The electron acceptor is micron activated carbon particles with a particle size of 100 μm-300 μm; The electron donor is nano-iron particles with a particle size of 20nm-100nm; The electron donor is loaded in the gaps of the electron acceptor.

2. A method for preparing a primary battery substrate capable of directionally generating free radicals according to claim 1, characterized in that: The following steps are involved: Step 1: mixing ferric chloride hexahydrate and micron activated carbon particles at a mass ratio of 1:0.4-0.6, dissolving the mixture in an ethanol aqueous solution, and mechanically stirring to obtain micron activated carbon particles with ferric chloride hexahydrate loaded in their pores; Step 2: In an oxygen-free environment, adding a reducing agent to the micron activated carbon particles with ferric chloride hexahydrate loaded in the pores, wherein the mass ratio of the reducing agent to the ferric chloride hexahydrate is 0.7-3.7:1, and magnetically stirring to reduce the ferric chloride hexahydrate to nano-iron particles, thereby obtaining micron activated carbon particles with nano-iron particles loaded in the pores; Step 3: In an oxygen-free environment, the micron activated carbon particles with nano-iron particles loaded in the pores are filtered, dried, and naturally cooled in sequence to obtain a primary battery substrate that can directionally generate free radicals.

3. The method for preparing a primary battery substrate capable of directionally generating free radicals according to claim 2, characterized in that: Step 1 is as follows: Step 1.1, mixing ethanol and water in a volume ratio of 3:6.5-7.5 to obtain an ethanol-water solution; Step 1.2, ferric chloride hexahydrate and micron activated carbon particles are mixed in a mass ratio of 1:0.4-0.6, and dissolved in an ethanol aqueous solution, wherein the mass ratio of the mixed particles to the ethanol aqueous solution is 1:50-80, and mechanical stirring is performed at a stirring speed of 90r / min-120r / min and a stirring time of 22h-24h to obtain micron activated carbon particles with ferric chloride hexahydrate loaded in the pores.

4. The method for preparing a primary battery substrate capable of directionally generating free radicals according to claim 3, characterized in that: In step 2: The oxygen-free environment is a nitrogen atmosphere; The magnetic stirring speed is 300r / min-400r / min, and the stirring time is 20min-30min; The reducing agent is sodium borohydride.

5. The method for preparing a primary battery substrate capable of directionally generating free radicals according to claim 3, characterized in that: Step 3 is as follows: In a vacuum filtration device, the micron activated carbon particles loaded with nano-iron particles in the pores are filtered and placed in a vacuum drying oven for drying at a temperature of 55°C to 60°C for 8 hours to 10 hours. The particles are then naturally cooled to room temperature to obtain a primary battery substrate capable of directionally generating free radicals.

6. A primary battery material capable of directionally generating free radicals, characterized in that: Composed of the primary battery substrate capable of directionally generating free radicals as claimed in claim 1 and metal nanoparticles; The mass percentage of the galvanic cell substrate capable of directionally generating free radicals is 95%-99%, and the remainder is metal nanoparticles; The metal nanoparticles are one of nano-copper particles, nano-manganese particles, and nano-lanthanum particles; The particle size of the metal nanoparticles is 20nm-100nm.

7. A method for preparing the primary battery material capable of directionally generating free radicals according to claim 6, characterized in that: The following steps are involved: Step 1: mixing the galvanic cell substrate capable of directionally generating free radicals according to claim 1 with a metal salt at a mass ratio of 25:1-10, dissolving the mixture in an ethanol aqueous solution, and stirring to obtain a galvanic cell substrate capable of directionally generating free radicals with the metal salt loaded in the pores; Wherein, the metal salt is one of copper sulfate pentahydrate, manganese chloride, and lanthanum nitrate hexahydrate; Step 2: Under anaerobic conditions, a reducing agent is added to the galvanic cell substrate capable of directionally generating free radicals and having metal salts loaded in the pores, wherein the mass ratio of the reducing agent to the metal salt in step 1 is 9-19:1, and magnetic stirring is performed to reduce the metal salt to metal nanoparticles, thereby obtaining a galvanic cell substrate capable of directionally generating free radicals and loaded with metal nanoparticles; Step 3: In an oxygen-free environment, the primary battery substrate capable of directionally generating free radicals and loaded with metal nanoparticles is filtered, dried, and naturally cooled in sequence to obtain a primary battery material capable of directionally generating free radicals.

8. The method for preparing a primary battery material capable of directionally generating free radicals according to claim 7, characterized in that: Step 1 is as follows: Step 1.1, mixing ethanol and water in a volume ratio of 3:6.5-7.5 to obtain an ethanol-water solution; Step 1.2, the primary battery substrate capable of directionally generating free radicals according to claim 1 is mixed with a metal salt in a mass ratio of 25:1-10 to obtain a mixed material, the mixed material is dissolved in an ethanol aqueous solution, the mass ratio of the mixed material to the ethanol aqueous solution is 1:100-200, and mechanical stirring is performed at a speed of 90r / min-120r / min and a stirring time of 22h-24h to obtain a primary battery substrate capable of directionally generating free radicals with a metal salt loaded in the pores; the metal salt is one of copper sulfate pentahydrate, manganese chloride, and lanthanum nitrate hexahydrate.

9. The method for preparing a primary battery material capable of directionally generating free radicals according to claim 7, characterized in that: In step 2: The oxygen-free condition is a nitrogen atmosphere; The reducing agent is sodium borohydride; The rotation speed of the magnetic stirring is 300r / min-400r / min, and the stirring time is 20min-30min.

10. The method for preparing a primary battery material capable of directionally generating free radicals according to claim 7, characterized in that: Step 3 is as follows: In a vacuum filtration device, the primary battery substrate capable of directionally generating free radicals loaded with metal nanoparticles is filtered and placed in a vacuum drying oven for drying at a temperature of 55°C to 60°C for 8 hours to 10 hours. The substrate is cooled to room temperature to obtain a primary battery material capable of directionally generating free radicals.

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