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CN-121976237-A - Preparation method and application of flexible kaolinite and graphite supported nickel-based catalyst

CN121976237ACN 121976237 ACN121976237 ACN 121976237ACN-121976237-A

Abstract

The invention discloses a preparation method and application of a flexible kaolinite and graphite supported nickel-based catalyst, relating to the technical field of electrocatalytic materials, wherein cellulose paper is used as a substrate, chitosan, kaolinite and graphene are uniformly dispersed in acetic acid solution, and adding nickel salt to form uniform impregnating solution, then impregnating cellulose paper therein, taking out and drying, and finally placing the cellulose paper into a tube furnace under inert atmosphere for high-temperature heating treatment to obtain the flexible kaolinite/graphite supported nickel-based catalyst. The method has simple process and low raw material cost, and the prepared material combines the high specific surface area of the kaolinite and the conductive enhancement effect of the graphene, has certain electrochemical activity and structural stability, and can be used in the field of electrocatalytic oxidation of 5-hydroxymethylfurfural.

Inventors

  • HAO XIAOFEI
  • WANG HAOHAO
  • ZHANG TAO
  • YUAN DONGLI
  • ZHANG RONGTAO
  • LIU XUPO

Assignees

  • 中国地质科学院郑州矿产综合利用研究所

Dates

Publication Date
20260505
Application Date
20260204

Claims (10)

  1. 1. The preparation method of the flexible kaolinite and graphite supported nickel-based catalyst is characterized by comprising the following steps: step S1, dissolving chitosan in an acetic acid solution, then respectively adding kaolinite and graphene into the acetic acid solution, and uniformly mixing by ultrasonic waves to obtain a solution A; step S2, slowly adding nickel chloride hexahydrate into the solution A for a plurality of times under magnetic stirring, and continuously stirring until the nickel salt is completely dissolved and a uniform blue-green solution is formed to obtain a solution B; S3, cutting the flexible substrate cellulose paper into a required size, immersing the flexible substrate cellulose paper into the solution B, taking out the flexible substrate cellulose paper after immersing, and draining to obtain a material C; S4, placing the material C in a blast drying oven for drying to obtain a material D; And S5, placing the material D into a tube furnace for heat treatment to obtain a target product catalyst E, namely the flexible kaolinite and the graphite supported nickel-based catalyst.
  2. 2. The preparation method of the flexible kaolinite and graphite supported nickel-based catalyst according to claim 1 is characterized in that in the step S1, the mass of chitosan solid is 0.1-1.0 g, the volume fraction of acetic acid solution is 1-10%, the mass of kaolinite and graphene is 10-100 mg respectively, and the ultrasonic time is 20-60 min.
  3. 3. The preparation method of the flexible kaolinite and graphite supported nickel-based catalyst according to claim 1, wherein the magnetic stirring speed in the step S2 is 300-800 rpm, the mass of the nickel chloride hexahydrate is 0.1-1 g, and the continuous stirring time is 2-10 h.
  4. 4. The method for preparing the flexible kaolinite-graphite supported nickel-based catalyst according to claim 1, wherein the mass of the nickel chloride hexahydrate in the step S2 is 0.1-1 g.
  5. 5. The method for preparing the flexible kaolinite-graphite supported nickel-based catalyst according to claim 1, wherein the cellulose paper in the step S3 has a size of (1-10) × (1-10) cm 2 and a dipping time of 20-60 min.
  6. 6. The method for preparing the flexible kaolinite and graphite supported nickel-based catalyst according to claim 1, wherein the drying temperature in the step S4 is 40-90 ℃ and the drying time is 2-8 h.
  7. 7. The method for preparing a flexible kaolinite and graphite supported nickel-based catalyst according to claim 1, characterized in that the heat treatment temperature in step S5 is 400-900 ℃.
  8. 8. The method for preparing a flexible kaolinite and graphite supported nickel-based catalyst according to claim 7, wherein the heating rate of the heat treatment in the step S5 is 3-5 ℃ per minute, and the heat treatment time is 1-3 hours.
  9. 9. The application of the flexible kaolinite and graphite supported nickel-based catalyst prepared by the preparation method of any one of claims 1-8 is characterized in that the flexible kaolinite and graphite supported nickel-based catalyst are used as working electrodes to form a three-electrode system, and the three-electrode system is applied to the preparation of2, 5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural in alkaline electrolyte.
  10. 10. The application of the flexible kaolinite and graphite supported nickel-based catalyst according to claim 9, wherein a platinum sheet and a mercury/mercury oxide electrode are used as a counter electrode and a reference electrode in the three-electrode system, an alkaline electrolyte is a KOH solution or a NaOH solution with the concentration of 5-hydroxymethylfurfural being 5-100 mmol/L, and the applied potential is 1.35-1.55V.

Description

Preparation method and application of flexible kaolinite and graphite supported nickel-based catalyst Technical Field The invention relates to the technical field of electrocatalytic materials, in particular to a preparation method and application of a flexible kaolinite and graphite supported nickel-based catalyst. Background Along with the increasing exhaustion of fossil resources and the aggravation of environmental pollution, the development of renewable bio-based polymer materials has become a global research hotspot. The 5-Hydroxymethylfurfural (HMF) is taken as an important biomass platform molecule, can be efficiently prepared by dehydrating carbohydrates such as fructose, glucose and the like, and is a key bridge for connecting biomass resources and high-added-value chemicals. HMF can be converted to 2, 5-furandicarboxylic acid (FDCA) by an oxidation reaction, which is a key monomer for the synthesis of bio-based polyester polyethylene furandicarboxylic acid (PEF). PEF has superior mechanical properties, gas barrier properties, and a lower carbon footprint compared to conventional petroleum-based polyethylene terephthalate (PET), and is considered to be an ideal substitute for PET. However, PEF industrial application faces a bottleneck, the core being that FDCA production costs are high. The traditional synthesis route relies on high-temperature and high-pressure noble metal catalytic oxidation, and has the advantages of high energy consumption, poor selectivity and serious equipment corrosion. In recent years, the electrocatalytic oxidation technology becomes a research hot spot for preparing FDCA by HMF oxidation due to the advantages of mild reaction conditions, controllable process, environmental protection and the like. However, the traditional nickel-based electrode (such as foam nickel) has the defects of rigid structure, easy corrosion and the like, limits the application of the electrode in a flexible electrolysis system, and is easy to generate surface passivation after long-term operation. Therefore, it is necessary to provide a method for preparing flexible kaolinite and graphite supported nickel-based catalyst and application thereof to solve the above problems. Disclosure of Invention The invention aims to solve the problems in the background art. The invention adopts the following technical scheme for realizing the purposes: The preparation method of the flexible kaolinite and graphite supported nickel-based catalyst comprises the following steps: step S1, dissolving chitosan in an acetic acid solution, then respectively adding kaolinite and graphene into the acetic acid solution, and uniformly mixing by ultrasonic waves to obtain a solution A; step S2, slowly adding nickel chloride hexahydrate into the solution A for a plurality of times under magnetic stirring, and continuously stirring until the nickel salt is completely dissolved and a uniform blue-green solution is formed to obtain a solution B; S3, cutting the flexible substrate cellulose paper into a required size, immersing the flexible substrate cellulose paper into the solution B, taking out the flexible substrate cellulose paper after immersing, and draining to obtain a material C; S4, placing the material C in a blast drying oven for drying to obtain a material D; And S5, placing the material D into a tube furnace for heat treatment to obtain a target product catalyst E, namely the flexible kaolinite and the graphite supported nickel-based catalyst. Further, in the step S1, the mass of chitosan solid is 0.1-1.0 g, the volume fraction of acetic acid solution is 1-10%, the mass of kaolinite and graphene are respectively 10-100 mg, and the ultrasonic time is 20-60 min. Further, in the step S2, the magnetic stirring rotating speed is 300-800 rpm, the mass of the nickel chloride hexahydrate is 0.1-1 g, and the continuous stirring time is 2-10 h. Further, the cellulose paper in the step S3 has a size of (1-10) × (1-10) cm 2 and a soaking time of 20-60 min. Further, in the step S4, the drying temperature is 40-90 ℃ and the drying time is 2-8 hours. Further, the temperature rising speed of the heat treatment in the step S5 is 3-5 ℃ per minute, the heat treatment time is 1-3h, and the heat treatment temperature is 400-900 ℃. The application of the flexible kaolinite and graphite supported nickel-based catalyst comprises the preparation method of the flexible kaolinite and graphite supported nickel-based catalyst, wherein the flexible kaolinite and graphite supported nickel-based catalyst are used as working electrodes to form a three-electrode system, and the application of the flexible kaolinite and graphite supported nickel-based catalyst in preparing 2, 5-furandicarboxylic acid by electrocatalytically oxidizing 5-hydroxymethylfurfural in alkaline electrolyte. Further, the three-electrode system is characterized in that a platinum sheet and a mercury/mercury oxide electrode are used as a counter electrode and a reference electro