Multi-component synergistic modified three-dimensional electro-catalytic material and preparation method thereof

Abstract

The invention discloses a multi-component synergistically modified three-dimensional electro-catalytic material and a preparation method thereof, and relates to the technical field of environmental catalytic materials.The material is prepared by taking columnar activated carbon as a carrier and synergistically loading cobalt-manganese-nickel-iron-copper-molybdenum-lanthanum-niobium multi-principal-element metal salt, acidic silica sol, phytic acid, a KH550 silane coupling agent and single-layer graphene oxide; all the components are compounded according to a specific mass ratio and are subjected to modification, impregnation and high-temperature curing. The preparation method comprises the steps of KH550 modified activated carbon preparation, multi-component composite steeping liquor preparation, co-adsorption / coating, air atmosphere high-temperature heat treatment and the like. According to the material, a three-dimensional structure of an activated carbon framework, a high-entropy active center and a Si-C-GO network is constructed, the material is applied to an MFEC heterogeneous catalytic electrolysis process to serve as a catalytic filler, and the technical problems that a traditional electro-catalytic material is narrow in pH adaptation range, poor in stability and low in mass transfer efficiency, and the treatment effect of refractory industrial wastewater is poor are solved. Good industrial application prospects are realized.

Description

Technical Field

[0001] This invention belongs to the field of environmental catalytic materials technology, specifically relating to a multi-component synergistic modified three-dimensional electrocatalytic material and its preparation method. Background Technology

[0002] Electrocatalytic oxidation technology is a core method for treating high-concentration, recalcitrant organic wastewater, widely used in wastewater treatment in industries such as chemical, pharmaceutical, papermaking, and mining. Its treatment effectiveness hinges on the performance of the electrocatalytic materials. Currently, traditional electrocatalytic electrode / packing materials generally suffer from three major technical defects: First, a narrow pH adaptability range; Fenton-type or metal oxide electrodes are prone to metal dissolution under strong acid or alkaline conditions, leading to rapid deactivation of catalytic activity. Second, poor structural stability; the active component has weak bonding with the carrier, making it prone to detachment, resulting in a short service life and increased industrial operating costs. Third, low mass transfer efficiency; two-dimensional planar electrodes have a small specific surface area and limited catalytic reaction sites, leading to poor treatment efficiency for high-COD, high-salinity wastewater.

[0003] To improve the performance of electrocatalytic materials, existing technologies employ optimization strategies such as high-entropy alloys, carbon material modification, and sol-gel methods. However, technical bottlenecks remain: poor dispersion of multiple components on the carrier surface makes it difficult to construct a three-dimensional structure with high conductivity, high activity, and high stability. Furthermore, for recalcitrant industrial wastewater containing vanillin, DMF, and tetrahydrofuran, characterized by complex composition, high COD concentration (tens of thousands to hundreds of thousands of mg / L), high salinity, and poor biodegradability, traditional processes such as precipitation, Fenton, and ozone achieve COD removal rates of less than 60%, failing to meet subsequent evaporator influent or discharge standards. Existing electrocatalytic materials are ill-suited to the treatment conditions of such wastewater, necessitating the development of an electrocatalytic material with wide pH adaptability, high stability, and high catalytic activity.

[0004] Furthermore, the existing MFEC multiphase catalytic electrolysis process, as an effective process for treating highly difficult wastewater, has performance limitations in its core supporting catalytic packing material, which leads to limited process treatment efficiency and stability. Therefore, developing a dedicated three-dimensional electrocatalytic material adapted to the MFEC process is of great industrial significance for improving the treatment efficiency of high-concentration, recalcitrant industrial wastewater. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] To address the problems mentioned in the background section, the present invention adopts the following technical solution.

[0007] A multi-component synergistic modified three-dimensional electrocatalytic material is constructed with columnar activated carbon as a substrate to form a three-dimensional porous framework structure. It is composed of the following components in mass percentage: 50-60% columnar activated carbon, 15-25% cobalt, manganese, nickel, iron, copper, molybdenum, lanthanum, and niobium multi-principal metal salts, 8-12% acidic silica sol with a solid content of 30%, 3-6% phytic acid, 2-4% KH550 silane coupling agent, and 2-5% monolayer graphene oxide solution with a concentration of 1 mg / mL. The multi-principal metal salts are one or a combination of two of the nitrates or acetates of cobalt, manganese, nickel, iron, copper, molybdenum, lanthanum, and niobium. Each metal is ionicly loaded onto the pores and surface of the columnar activated carbon. The three-dimensional electrocatalytic material is HEA@AC-GO / Si-P-KH550, forming a multi-level porous structure of "activated carbon framework + high-entropy active center + Si-C-GO network".

[0008] Preferably, the three-dimensional electrocatalytic material can operate stably within the pH range of 2-10, with a metal leaching concentration of <0.1ppm, and a continuous service life of ≥3 years (>26000 hours) under actual operating conditions; the COD removal rate for recalcitrant organic pollutants is ≥85%, and the activity retention rate is ≥92% after 10 continuous catalytic cycles.

[0009] Preferably, the columnar activated carbon has a particle size of 3-5 mm, a large specific surface area, and excellent electrical conductivity. After pretreatment, the surface is free of impurities and ash, providing a stable substrate for loading active components. The monolayer graphene oxide solution uses deionized water as the dispersion medium, which prevents agglomeration and effectively bridges the metal active centers and the activated carbon substrate.

[0010] Preferably, the molar ratio of each metal ion in the cobalt-manganese-nickel-iron-copper-molybdenum-lanthanum-niobium multi-principal metal salt is Co 2+ :Mn 2 + :Ni 2+ :Fe 3+ :Cu 2+ :Mo 6+ :La 3+ :Nb 5+ =1:(0.5-0.8):1:1:(0.2-0.3):(0.2-0.3):(0.2-0.4), the total concentration of multi-principal metal ions is 0.2mol / L, which can construct high-entropy oxide active centers and provide abundant redox couples.

[0011] A method for preparing a multi-component synergistically modified three-dimensional electrocatalytic material based on the above-mentioned technical solution includes four main steps: preparation of KH550 modified activated carbon, preparation of multi-component composite impregnation solution, co-adsorption / coating of active components, and high-temperature curing in air atmosphere. Specifically: S1. Preparation of modified activated carbon: After acid washing, water washing and drying, columnar activated carbon is immersed in an ethanol-water solution containing KH550 for surface modification, and after filtration and drying, KH550 modified activated carbon is obtained. S2. Preparation of multi-component composite impregnation solution: After dissolving multi-principal metal salts in a specific molar ratio, phytic acid, acidic silica sol, and monolayer graphene oxide dispersion are added sequentially, and a uniform composite impregnation solution is obtained by stirring and ultrasonic dispersion. S3. Co-adsorption and coating: KH550 modified activated carbon and composite impregnation liquid are mixed at a specific liquid-solid ratio for adsorption, or the impregnation liquid is coated on the surface of modified activated carbon by spraying / brushing, so that the active components are loaded onto the activated carbon. S4. High-temperature curing treatment: Activated carbon loaded with active components is placed in a tube furnace and subjected to programmed heating and heat treatment in an air atmosphere. After natural cooling, the multi-component synergistic modified three-dimensional electrocatalytic material is obtained.

[0012] Preferably, in step S1, the acid washing involves soaking the columnar activated carbon in 1 mol / L dilute hydrochloric acid for 2 hours, washing it with water until neutral, and then drying it at a constant temperature of 60°C. The ethanol-water solution contains 5% KH550 by mass, the pH of the solution is adjusted to 4 with glacial acetic acid, the impregnation modification time is 12 hours, and after modification, it is dried at a constant temperature of 80°C for 2 hours to ensure that KH550 is fully grafted onto the surface of the activated carbon.

[0013] Preferably, the molar ratio of phytic acid to multi-principal metal ions in S2 is 1:1, so that the phytic acid can fully complex the metal ions and prevent them from precipitating prematurely; the stirring speed is 300-500 r / min and the stirring time is 20-30 min; the subsequent ultrasonic dispersion power is 300-400 W and the ultrasonic dispersion time is 30 min, to ensure that the components of the composite impregnation solution are uniformly dispersed.

[0014] Preferably, the liquid-solid ratio of the composite impregnation solution in S3 to the KH550 modified activated carbon is (0.5-0.8):1 (mL / g), the stirring speed at room temperature is 200-300 r / min, and the adsorption time is 6 h, so that the active components are fully adsorbed into the pores and surface of the activated carbon; if spraying / brushing is used, the spraying pressure is 0.2-0.4 MPa, and the brushing is done 2-3 times to ensure uniform loading of the active components.

[0015] In step S4, the temperature rise rate is 5℃ / min, and after the temperature is raised to 300℃, it is held for heat treatment for 2 hours. The gas flow rate of the air atmosphere is 0.5-1L / min. During the heat treatment, phytic acid carbonization, silica sol film formation and metal salt oxidation are realized simultaneously to construct a stable Si-C-GO network structure.

[0016] The specific application of the aforementioned multi-component synergistic modified three-dimensional electrocatalytic material in this application is as follows: the material is used as a special catalytic filler in the MFEC multiphase catalytic electrolysis process, in conjunction with special electrode plates, to treat high-concentration, recalcitrant industrial wastewater in the pH range of 2-10; the industrial wastewater includes one or more of the following: caprolactam wastewater, vanillin wastewater, DMF wastewater, tetrahydrofuran wastewater, fluorescent wastewater, DMAC wastewater, pharmaceutical wastewater, and papermaking wastewater, with an influent COD of 260-209400 mg / L, and a COD removal rate ≥73% after MFEC treatment, of which the COD removal rate of high-COD industrial wastewater (COD≥10000 mg / L) is ≥85%.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) In this invention, columnar activated carbon is used as the macroscopic three-dimensional framework, silica sol and phytic acid carbonization layer form a mesoporous network, graphene oxide bridges the carrier and active center, forming a multi-level pore structure with a large specific surface area and abundant catalytic reaction sites, which significantly improves mass transfer efficiency and is suitable for the treatment of high-concentration wastewater.

[0018] (2) In this invention, the SiO2-carbon-metal oxide composite layer effectively isolates acid and alkali corrosion, and the entropy stabilization effect of the high-entropy metal oxide inhibits the dissolution of a single metal. The material can operate stably in the pH range of 2-10, and the metal dissolution concentration is <0.1ppm. Accelerated aging experiments show that the service life can reach more than 3 years (>26000 hours) under actual working conditions, and the catalytic activity retention rate is >92% after 10 consecutive cycles of operation.

[0019] (3) The high-entropy active center constructed by the multi-principal metal salt in this invention can synergistically activate water molecules to generate a variety of strong oxidizing active species. Graphene oxide improves electron conduction efficiency and has a COD removal rate of >95% for refractory organic compounds such as phenol, dyes, and antibiotics. When applied to the MFEC process, the COD removal rate of industrial wastewater such as vanillin, DMF, and tetrahydrofuran is all above 85%. For example, after treatment, the COD of vanillin wastewater (COD 10000 mg / L) is reduced to 1080 mg / L, and the COD of DMF wastewater (COD 98850 mg / L) is reduced to 8150 mg / L.

[0020] (4) The preparation method of the present invention adopts conventional chemical processes such as impregnation and heat treatment. The steps are simple, the process parameters are easy to control, no complex equipment is required, and industrial mass production can be realized. At the same time, the material has good regenerability and can restore catalytic activity through simple cleaning, reducing industrial operating costs. Furthermore, the material can be used as a special catalytic packing for MFEC process. It can be used in conjunction with special plates to treat a variety of high-concentration and difficult-to-degrade industrial wastewater such as caprolactam, vanillin, DMF, tetrahydrofuran, fluorescent wastewater, and papermaking wastewater. This solves the problem of insufficient performance of existing MFEC process matching packing. Moreover, the treated wastewater can meet the evaporator inlet water requirements and improve the efficiency of wastewater resource utilization. Detailed Implementation

[0021] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below.

[0022] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0023] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places throughout this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that mutually excludes other embodiments. The present invention provides the following embodiments.

[0024] Example 1: Preparation of multi-component synergistically modified three-dimensional electrocatalytic materials 1. Take 100g of columnar activated carbon with a particle size of 3-5mm, soak it in 1mol / L dilute hydrochloric acid for 2h, wash it with deionized water until neutral, and dry it at 60℃; prepare a 5wt% KH550 ethanol-water solution (adjust pH=4 with glacial acetic acid), soak the activated carbon in it for 12h, filter it, and dry it at 80℃ for 2h to obtain KH550 modified activated carbon.

[0025] 2. Press Co 2+ :Mn 2+ :Ni 2+ :Fe 3+ :Cu 2+ :Mo 6+ :La 3+ :Nb 5+The molar ratio of 1:0.6:1:1:0.25:0.25:0.3 was used to weigh out the corresponding nitrates and dissolve them in deionized water to prepare 500 mL of a solution with a total metal ion concentration of 0.2 mol / L. 1.5 g of phytic acid was added and stirred to dissolve. Then, 40 mL of acidic silica sol with a solid content of 30% and 30 mL of monolayer graphene oxide dispersion with a concentration of 1 mg / mL were added. The mixture was ultrasonically dispersed for 30 min to obtain the composite impregnation solution.

[0026] 3. Immerse KH550 modified activated carbon in a composite impregnation solution with a liquid-to-solid ratio of 0.6:1 (mL / g) and stir at room temperature for 6 hours for adsorption.

[0027] 4. The adsorbed activated carbon was placed in a tube furnace and heated to 300℃ at 5℃ / min in an air atmosphere, held for 2 hours, and then naturally cooled to obtain the three-dimensional electrocatalytic material HEA@AC-GO / Si-P-KH550. The mass percentage of each component was as follows: columnar activated carbon 55%, multi-principal metal salt 20%, acidic silica sol 10%, phytic acid 5%, KH550 3%, and monolayer graphene oxide solution 4%.

[0028] Example 2: Performance testing of three-dimensional electrocatalytic materials The three-dimensional electrocatalytic material prepared in Example 1 was subjected to pH adaptability and stability tests: 1. pH adaptability test: Phenol simulated wastewater (COD=600mg / L) was prepared and the pH was adjusted to 3, 7 and 10 respectively. The material was used as the catalytic packing for the MFEC process, with graphite plates as the anode and cathode, and the current density was 20mA / cm², and the electrolysis was carried out for 30min. The test results were as follows: COD removal rate was 98.2% at pH=3, 96.5% at pH=7 and 85.1% at pH=10, all of which showed excellent catalytic activity.

[0029] 2. Stability Test: The above-mentioned phenol simulated wastewater treatment experiment at pH=3 was repeated for 10 cycles, and the catalytic activity of the material was maintained at 93.5%. After accelerated aging tests at 50℃, pH=2, and pH=12, the estimated service life of the material under actual working conditions can reach 3.2 years, and the metal leaching concentration was detected as 0.08ppm < 0.1ppm.

[0030] Example 3: Application of three-dimensional electrocatalytic materials in vanillin wastewater treatment The three-dimensional electrocatalytic material prepared in Example 1 was used as a catalytic packing material in the MFEC heterogeneous catalytic electrolysis process for treating vanillin wastewater. The specific process is as follows: 1. Wastewater quality: COD=10000mg / L, color 1000 times, total salt 10% (mainly sodium sulfate), pH 6-7, poor biodegradability; 2. MFEC process parameters: The equipment is designed to have an influent flow rate of 2.5L / h. After adding 12ml of oxidation initiator, the equipment is electrolyzed for 2.5h after aeration and stirring. The effluent is then treated with 50ppm of high-efficiency coagulant and 10ppm of 12 million molecular weight anionic PAM for coagulation and sedimentation. 3. Treatment effect: The COD of the effluent was reduced to 1080mg / L, the COD removal rate was 89.2%, the color was reduced by 300 times, the operating cost per ton of water was 27.35 yuan, and the treated wastewater met the requirements of the evaporator inlet water.

[0031] Example 4: Application of three-dimensional electrocatalytic materials in DMF wastewater treatment The three-dimensional electrocatalytic material prepared in Example 1 was used as a catalytic packing material in the MFEC process for treating DMF wastewater. The specific process is as follows: 2. Wastewater quality: COD=98850mg / L, pH1-2 (strongly acidic), strong odor; 2. MFEC process parameters: Take 0.5L of raw water, add alkali to adjust the pH to 3, put it into the MFEC reaction tank, turn on the circulation pump to stir, electrolyze for 2 hours, and add 10ppm of 12 million molecular weight anionic PAM for coagulation and precipitation in the effluent. 3. Treatment effect: The COD of the effluent was reduced to 8150 mg / L, the COD removal rate was 91.7%, no metal leaching occurred under strong acid modification conditions, and the catalytic activity was stable.

[0032] Example 5: Application of three-dimensional electrocatalytic materials in the treatment of various industrial wastewaters The three-dimensional electrocatalytic material prepared in Example 1 was applied to the MFEC process to treat industrial wastewater from tetrahydrofuran, fluorescence, papermaking, and mining, respectively. The treatment effects are shown in Table 1. Table 1. Treatment efficiency of MFEC process for various types of industrial wastewater .

[0033] As can be seen from Table 1, the three-dimensional electrocatalytic material of the present invention has good treatment effect on industrial wastewater of different concentrations and under different working conditions. It has strong adaptability and can be widely used in wastewater treatment in industries such as chemical, pharmaceutical, papermaking, and mining.

[0034] In summary, the preparation method of the multi-component synergistic modified three-dimensional electrocatalytic material of this invention is simple and easy to scale up industrially. The material has the technical characteristics of wide pH adaptability, high stability, and high catalytic activity. It can be used as a special catalytic packing material for MFEC heterogeneous catalytic electrolysis process and can be widely used in the treatment of various high-concentration and recalcitrant industrial wastewater such as caprolactam, vanillin, DMF, tetrahydrofuran, fluorescent wastewater, and papermaking wastewater. The COD removal rate can reach more than 85%, and the treated wastewater can meet the requirements of evaporator influent or subsequent biochemical treatment. At the same time, the material has a long service life and good regenerability, which greatly reduces industrial operating costs and has good industrial promotion value and market application prospects.

[0035] The above description, in conjunction with specific embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, several simple deductions or substitutions can be made without departing from the concept of the present invention, and all such deductions or substitutions should be considered to fall within the scope of protection defined by the claims submitted herein.

Claims

1. A multi-component synergistically modified three-dimensional electrocatalytic material, characterized in that, A three-dimensional porous framework structure is constructed using columnar activated carbon as a substrate, which is synergistically composed of the following components by mass percentage: 50-60% columnar activated carbon, 15-25% cobalt, manganese, nickel, iron, copper, molybdenum, lanthanum, and niobium multi-principal metal salts, 8-12% acidic silica sol with a solid content of 30%, 3-6% phytic acid, 2-4% KH550 silane coupling agent, and 2-5% monolayer graphene oxide solution with a concentration of 1 mg / mL. The multi-principal metal salts are one or a combination of two of the nitrates or acetates of cobalt, manganese, nickel, iron, copper, molybdenum, lanthanum, and niobium, and each metal is ionicly loaded on the pores and surface of the columnar activated carbon. The three-dimensional electrocatalytic material is HEA@AC-GO / Si-P-KH550, forming a multi-level porous structure of "activated carbon framework + high-entropy active center + Si-C-GO network".

2. The multi-component synergistically modified three-dimensional electrocatalytic material according to claim 1, characterized in that: The three-dimensional electrocatalytic material can operate stably in the pH range of 2-10, with a metal leaching concentration of <0.1ppm and a continuous service life of ≥3 years (>26,000 hours) under actual working conditions; the COD removal rate of recalcitrant organic pollutants is ≥85%, and the activity retention rate is ≥92% after 10 continuous catalytic cycles.

3. The multi-component synergistically modified three-dimensional electrocatalytic material according to claim 2, characterized in that: The columnar activated carbon has a particle size of 3-5 mm, a large specific surface area, and excellent electrical conductivity. After pretreatment, the surface is free of impurities and ash, providing a stable substrate for loading active components. The monolayer graphene oxide solution uses deionized water as the dispersion medium, which does not exhibit agglomeration and can effectively bridge the metal active centers and the activated carbon substrate.

4. The multi-component synergistically modified three-dimensional electrocatalytic material according to claim 1, characterized in that: The molar ratio of each metal ion in the cobalt-manganese-nickel-iron-copper-molybdenum-lanthanum-niobium multi-principal metal salt is Co 2+ :Mn 2+ :Ni 2+ :Fe 3+ :Cu 2+ :Mo 6+ :La 3+ :Nb 5+ =1:(0.5-0.8):1:1:(0.2-0.3):(0.2-0.3):(0.2-0.4), the total concentration of multi-principal metal ions is 0.2mol / L, which can construct high-entropy oxide active centers and provide abundant redox couples.

5. A method for preparing the multi-component synergistically modified three-dimensional electrocatalytic material as described in claim 1, characterized in that, The process includes four main steps: preparation of KH550 modified activated carbon, formulation of multi-component composite impregnation solution, co-adsorption / coating of active components, and high-temperature curing in air atmosphere. S1. Preparation of modified activated carbon: After acid washing, water washing and drying, columnar activated carbon is immersed in an ethanol-water solution containing KH550 for surface modification, and after filtration and drying, KH550 modified activated carbon is obtained. S2. Preparation of multi-component composite impregnation solution: After dissolving multi-principal metal salts in a specific molar ratio, phytic acid, acidic silica sol, and monolayer graphene oxide dispersion are added sequentially, and a uniform composite impregnation solution is obtained by stirring and ultrasonic dispersion. S3. Co-adsorption and coating: KH550 modified activated carbon and composite impregnation liquid are mixed at a specific liquid-solid ratio for adsorption, or the impregnation liquid is coated on the surface of modified activated carbon by spraying / brushing, so that the active components are loaded onto the activated carbon. S4. High-temperature curing treatment: Activated carbon loaded with active components is placed in a tube furnace and subjected to programmed heating and heat treatment in an air atmosphere. After natural cooling, the multi-component synergistic modified three-dimensional electrocatalytic material is obtained.

6. The method for preparing the multi-component synergistically modified three-dimensional electrocatalytic material according to claim 5, characterized in that: In step S1, the acid washing involves soaking columnar activated carbon in 1 mol / L dilute hydrochloric acid for 2 hours, washing it with water until neutral, and then drying it at a constant temperature of 60°C. The ethanol-water solution contains 5% KH550 by mass, and the pH of the solution is adjusted to 4 with glacial acetic acid. The impregnation modification time is 12 hours, and after modification, the solution is dried at a constant temperature of 80°C for 2 hours to ensure that KH550 is fully grafted onto the surface of the activated carbon.

7. The method for preparing the multi-component synergistically modified three-dimensional electrocatalytic material according to claim 6, characterized in that: In step S2, the molar ratio of phytic acid to multi-principal metal ions is 1:1, and the phytic acid fully complexes the metal ions to prevent them from precipitating prematurely. The stirring speed is 300-500 r / min, and the stirring time is 20-30 min. The subsequent ultrasonic dispersion power is 300-400 W, and the ultrasonic dispersion time is 30 min to ensure that the components of the composite impregnation solution are uniformly dispersed.

8. The method for preparing the multi-component synergistically modified three-dimensional electrocatalytic material according to claim 5, characterized in that: In step S3, the liquid-solid ratio of the composite impregnation solution to the KH550 modified activated carbon is (0.5-0.8):1 (mL / g). The stirring speed at room temperature is 200-300 r / min, and the adsorption time is 6 h, so that the active components are fully adsorbed into the pores and surface of the activated carbon. If spraying / brushing is used, the spraying pressure is 0.2-0.4 MPa, and the brushing is done 2-3 times to ensure uniform loading of the active components.

9. The method for preparing the multi-component synergistically modified three-dimensional electrocatalytic material according to claim 5, characterized in that: In step S4, the temperature rise rate is 5℃ / min, and after the temperature is raised to 300℃, it is held for heat treatment for 2 hours. The gas flow rate of the air atmosphere is 0.5-1L / min. During the heat treatment, phytic acid carbonization, silica sol film formation and metal salt oxidation are realized simultaneously to construct a stable Si-C-GO network structure.

10. The application of the multi-component synergistically modified three-dimensional electrocatalytic material according to claim 1, characterized in that, The aforementioned material is used as a dedicated catalytic filler in the MFEC multiphase catalytic electrolysis process, in conjunction with special electrode plates, to treat high-concentration, recalcitrant industrial wastewater in the pH range of 2-10. The industrial wastewater includes one or more of the following: caprolactam wastewater, vanillin wastewater, DMF wastewater, tetrahydrofuran wastewater, fluorescent wastewater, DMAC wastewater, pharmaceutical wastewater, and papermaking wastewater. The influent COD is 260-209400 mg / L, and the COD removal rate after MFEC treatment is ≥73%, of which the COD removal rate of high-COD industrial wastewater (COD≥10000 mg / L) is ≥85%.