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CN-121972183-A - Multicomponent synergistic modified three-dimensional electrocatalytic material and preparation method thereof

CN121972183ACN 121972183 ACN121972183 ACN 121972183ACN-121972183-A

Abstract

The invention discloses a multi-component synergistic modified three-dimensional electrocatalytic material and a preparation method thereof, relating to the technical field of environmental catalytic materials, wherein the material takes columnar active carbon as a carrier, the synergistic supported cobalt-manganese-nickel-iron-copper-molybdenum-lanthanum-niobium multi-principal element metal salt, acidic silica sol, phytic acid, KH550 silane coupling agent and single-layer graphene oxide are compounded according to a specific mass ratio, and the synergistic supported cobalt-manganese-nickel-iron-copper-molybdenum-lanthanum-niobium multi-principal element metal salt is prepared through modification, impregnation and high-temperature curing. The preparation method comprises the steps of KH550 modified activated carbon preparation, multi-component composite impregnating solution preparation, co-adsorption/coating, air atmosphere high temperature heat treatment and the like. The material builds a three-dimensional structure of an active carbon skeleton, a high-entropy active center and a Si-C-GO network, and is applied to an MFEC heterogeneous catalytic electrolysis process as a catalytic filler, so that the technical problems of narrow pH application range, poor stability, low mass transfer efficiency and poor degradation-resistant industrial wastewater treatment effect of the traditional electrocatalytic material are solved, and the material has a good industrial application prospect.

Inventors

  • SHI XIAOCHEN

Assignees

  • 三益智碳(无锡)科技有限公司

Dates

Publication Date
20260505
Application Date
20260309

Claims (10)

  1. 1. A multi-component synergistic modified three-dimensional electrocatalytic material is characterized in that a three-dimensional porous skeleton structure is constructed by taking columnar active carbon as a substrate, the three-dimensional porous skeleton structure is formed by synergistically compounding, by mass, 50-60% of columnar active carbon, 15-25% of cobalt-manganese-nickel-iron-copper-molybdenum-lanthanum-niobium multi-principal metal salt, 8-12% of acidic silica sol with 30% of solid content, 3-6% of phytic acid, 2-4% of KH550 silane coupling agent and 2-5% of single-layer graphene oxide solution with the concentration of 1mg/mL, the multi-principal metal salt is one or two of nitrate or acetate of cobalt, manganese, nickel, iron, copper, molybdenum, lanthanum and niobium, each metal is loaded on the pore and the surface of the columnar active carbon in an ionic form, and the three-dimensional electrocatalytic material is HEA@AC-GO/Si-P-KH550, so that a multi-pore structure of an active carbon skeleton+high active center+Si-C-GO network is formed.
  2. 2. The multi-component synergistic modified three-dimensional electrocatalytic material as set forth in claim 1, wherein the three-dimensional electrocatalytic material can stably operate within a pH range of 2-10, the metal dissolution concentration is less than 0.1ppm, the continuous service life is more than or equal to 3 years (> 26000 hours) under practical conditions, the COD removal rate of refractory organic pollutants is more than or equal to 85%, and the activity retention rate after 10 continuous operation cycles is more than or equal to 92%.
  3. 3. The multi-component synergistic modified three-dimensional electrocatalytic material of claim 2, wherein the columnar activated carbon has a particle size of 3-5mm, a large specific surface area and excellent conductivity, the pretreated surface has no impurity or ash, a stable substrate is provided for loading active components, and the single-layer graphene oxide solution takes deionized water as a dispersion medium, has no agglomeration phenomenon, and can effectively bridge a metal active center and an activated carbon substrate.
  4. 4. The multi-component synergistically modified three-dimensional electrocatalytic material of claim 1, wherein the molar ratio of metal ions 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), and the total concentration of the multi-principal metal ions is 0.2mol/L, so that a high-entropy oxide active center can be constructed, and rich redox couple can be provided.
  5. 5. The preparation method of the multi-component synergistic modified three-dimensional electrocatalytic material as set forth in claim 1, which is characterized by comprising four steps of KH550 modified activated carbon preparation, multi-component composite impregnating solution preparation, active component co-adsorption/coating and air atmosphere high-temperature curing in sequence, specifically comprising the following steps: S1, preparing modified activated carbon, namely pickling, washing and drying columnar activated carbon, immersing the columnar activated carbon in ethanol-water solution containing KH550 for surface modification, and filtering and drying to obtain KH550 modified activated carbon; s2, preparing a multi-component composite impregnating solution, namely dissolving multi-principal element metal salt according to a specific molar ratio, sequentially adding phytic acid, acidic silica sol and single-layer graphene oxide dispersion liquid, and stirring and performing ultrasonic dispersion to prepare a uniform composite impregnating solution; S3, co-adsorption and coating, namely mixing KH550 modified activated carbon with the composite impregnating solution according to a specific liquid-solid ratio for adsorption, or coating the impregnating solution on the surface of the modified activated carbon in a spraying/brushing mode to load active components on the activated carbon; s4, high-temperature solidification treatment, namely placing active carbon loaded with active components in a tube furnace, programming temperature in an air atmosphere, carrying out heat preservation heat treatment, and naturally cooling to obtain the multi-component synergistic modified three-dimensional electrocatalytic material.
  6. 6. The preparation method of the multi-component synergistic modified three-dimensional electrocatalytic material as set forth in claim 5, wherein in the step S1, the cylindrical activated carbon is soaked in 1mol/L dilute hydrochloric acid for 2 hours, washed to be neutral with water and then dried at a constant temperature of 60 ℃, the mass fraction of KH550 in the ethanol-water solution is 5%, the pH of the solution is regulated to 4 by glacial acetic acid, the soaking modification time is 12 hours, and the modified activated carbon is dried at a constant temperature of 80 ℃ for 2 hours, so that KH550 is fully grafted on the surface of the activated carbon.
  7. 7. The preparation method of the multi-component synergistic modified three-dimensional electrocatalytic material as set forth in claim 6, wherein in the step S2, the mole ratio of the phytic acid to the multi-principal metal ions is 1:1, the phytic acid is fully complexed with the metal ions to prevent the metal ions from precipitating in advance, the stirring and dissolving rotating speed is 300-500r/min, the stirring time is 20-30min, the power of the subsequent ultrasonic dispersion is 300-400W, the ultrasonic dispersion time is 30min, and the uniform dispersion of each component of the composite impregnating solution is ensured.
  8. 8. The preparation method of the multi-component synergistic modified three-dimensional electrocatalytic material as set forth in claim 5, wherein in the step S3, the liquid-solid ratio of the composite impregnating solution to the KH550 modified active carbon is (0.5-0.8): 1 (mL/g), the stirring and adsorbing speed at normal temperature is 200-300r/min, the adsorbing time is 6h, the active components are fully adsorbed on the pore channels and the surface of the active carbon, and if a spraying/brushing mode is adopted, the spraying pressure is 0.2-0.4MPa, the brushing times are 2-3 times, and the uniform loading of the active components is ensured.
  9. 9. The preparation method of the multi-component synergistic modified three-dimensional electrocatalytic material as set forth in claim 5, wherein in the step S4, the temperature-programmed heating rate is 5 ℃ per minute, the heat treatment is carried out for 2 hours after the temperature is raised to 300 ℃, the gas flow rate of the air atmosphere is 0.5-1L/min, and the phytic acid carbonization, the silica sol film formation and the metal salt oxidation are synchronously realized in the heat treatment process, so that a stable Si-C-GO network structure is constructed.
  10. 10. The application of the multi-component synergistic modified three-dimensional electrocatalytic material as claimed in claim 1, wherein the material is used as a special catalytic filler in an MFEC multiphase catalytic electrolysis process and is matched with a special polar plate to treat high-concentration nondegradable industrial wastewater with pH ranging from 2 to 10, wherein the industrial wastewater comprises one or more of caprolactam wastewater, vanillin wastewater, DMF wastewater, tetrahydrofuran wastewater, fluorescent wastewater, DMAC wastewater, pharmaceutical wastewater and papermaking wastewater, the COD of inflow water is 260-209700 mg/L, the COD removal rate of the high COD industrial wastewater (COD is more than or equal to 10000 mg/L) is more than or equal to 73% after being treated by the MFEC process, and the COD removal rate of the high COD industrial wastewater (COD is more than or equal to 10000 mg/L) is more than or equal to 85%.

Description

Multicomponent synergistic modified three-dimensional electrocatalytic material and preparation method thereof Technical Field The invention belongs to the technical field of environmental catalytic materials, and particularly relates to a multi-component synergistic modified three-dimensional electrocatalytic material and a preparation method thereof. Background The electrocatalytic oxidation technology is a core means for treating high-concentration and difficult-to-degrade organic wastewater, and is widely applied to wastewater treatment in the industries of chemical industry, pharmacy, papermaking, mining and the like, and the core of the treatment effect depends on the performance of electrocatalytic materials. At present, the traditional electrocatalytic electrode/filler material has three general technical defects of narrow pH adaptation range, easy metal dissolution of Fenton type or metal oxide electrode under strong acid and strong alkali conditions, quick inactivation of catalytic activity, poor structural stability, weak binding force between active components and carriers, easy falling off, short service life, increased industrial operation cost, low mass transfer efficiency, small specific surface area of two-dimensional planar electrode, limited catalytic reaction sites and poor treatment efficiency on high COD and high salinity wastewater. In order to improve the performance of the electrocatalytic material, the prior art adopts strategies such as high-entropy alloy, carbon material modification, sol-gel method and the like for optimization, but has the technical bottlenecks that the dispersibility of multiple components on the surface of a carrier is poor, a three-dimensional structure with high conductivity, high activity and high stability is difficult to construct, meanwhile, aiming at industrial wastewater which is difficult to degrade such as vanillin, DMF, tetrahydrofuran and the like, the components are complex, the COD concentration is high (up to tens of thousands to twenty thousand mg/L), the salinity is high, the biodegradability is poor, the COD removal rate of the traditional processes such as precipitation, fenton, ozone and the like is less than 60 percent, the requirements of the water inlet or discharge standard of a subsequent evaporator cannot be met, and the existing electrocatalytic material is difficult to adapt to the treatment working conditions of the wastewater, so that the electrocatalytic material with wide pH adaptability, high stability and high catalytic activity is required to be developed. In addition, the existing MFEC multiphase catalytic electrolysis process is used as an effective process for treating high-difficulty wastewater, and the catalytic filler matched with the core of the existing MFEC multiphase catalytic electrolysis process has a short performance plate, so that the process treatment effect and stability are limited, and therefore, the development of a special three-dimensional electrocatalytic material suitable for the MFEC process has important industrial significance for improving the treatment efficiency of high-concentration refractory industrial wastewater. Disclosure of Invention This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application. In order to solve the problems set forth in the background art, the present invention adopts the following technical scheme. A multi-component synergistic modified three-dimensional electrocatalytic material is formed by constructing a three-dimensional porous skeleton structure by taking columnar active carbon as a substrate, and is formed by synergistically compounding, by mass, 50-60% of columnar active carbon, 15-25% of cobalt-manganese-nickel-iron-copper-molybdenum-lanthanum-niobium multi-principal metal salt, 8-12% of acidic silica sol with 30% of solid content, 3-6% of phytic acid, 2-4% of KH550 silane coupling agent and 2-5% of single-layer graphene oxide solution with the concentration of 1mg/mL, wherein the multi-principal metal salt is one or two of nitrate or acetate of cobalt, manganese, nickel, iron, copper, molybdenum, lanthanum and niobium, and each metal is loaded on the pore and the surface of the columnar active carbon in an ionic form, and the three-dimensional electrocatalytic material is HEA@AC-GO/Si-P-KH550, so that a multi-pore structure of an active carbon skeleton+a high-entropy active center+Si-C-network is formed. Preferably, the three-dimensional electrocatalytic material can stably run within the pH range of 2-10, the metal dissolution concentration is less than 0.1ppm, the continuous service life is more than or equal to 3 years (> 26000 hours) under the actual working condition, the COD re