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CN-121992445-A - Amidoxime modified iron/titanium bimetal doped carbon electrode and preparation method and application thereof

CN121992445ACN 121992445 ACN121992445 ACN 121992445ACN-121992445-A

Abstract

The invention relates to the technical field of electrochemical uranium extraction, in particular to an amidoxime-modified iron/titanium bimetal doped carbon electrode, and a preparation method and application thereof. The preparation method comprises the steps of mixing 2-amino terephthalic acid, N-dimethylformamide, methanol, tetrabutyl titanate and acetic acid, performing heat treatment to obtain Ti-MOF, mixing the Ti-MOF and water, then placing the mixture into a composite solution consisting of ferrous acetate, 1, 10-phenanthroline, ethanol and water for reaction, then sequentially performing carbonization reduction reaction and nitridation reaction, mixing the obtained Fe/TiO x /C with polyacrylonitrile, azodiisobutyronitrile and N, N-dimethylformamide in an oil bath, adding hydroxylamine hydrochloride and sodium carbonate, performing amidoximation reaction, and coating the obtained carbon material on a graphite felt to obtain the electrode. The electrode prepared by the invention can improve the uranium extraction rate to 90% only under the voltage of-0.9V on the premise of adopting a penetrating type electrolytic tank, thereby greatly reducing the energy consumption.

Inventors

  • TIAN XINLONG
  • HUANG XIN
  • Xue beichen
  • LIU YAOWEN
  • YI HAITAO
  • JI YILIN
  • YANG DONGJIN

Assignees

  • 海南大学

Dates

Publication Date
20260508
Application Date
20260310

Claims (10)

  1. 1. A method for preparing an amidoxime-modified iron/titanium bimetallic doped carbon electrode, which is characterized by comprising the following steps: s1, mixing 2-amino terephthalic acid, N-dimethylformamide, methanol and tetrabutyl titanate, performing ultrasonic treatment to obtain a suspension, and adding acetic acid into the suspension for heat treatment to obtain Ti-MOF; S2, mixing ferrous acetate, 1, 10-phenanthroline, ethanol and water to obtain a composite solution; s3, mixing the Ti-MOF with water to obtain a Ti-MOF solution, and placing the Ti-MOF solution into a composite solution for reaction to obtain an intermediate product; S4, performing carbonization reduction reaction on the intermediate product in an argon atmosphere, then performing nitridation reaction in an ammonia atmosphere, and cooling to obtain Fe/TiO x /C; S5, mixing Fe/TiO x /C, polyacrylonitrile, azodiisobutyronitrile and N, N-dimethylformamide, carrying out oil bath, dispersing an oil bath product in water, adding hydroxylamine hydrochloride and sodium carbonate, and carrying out amidoxime reaction to obtain an amidoxime modified iron/titanium bimetal doped carbon material; S6, coating the amidoxime-modified iron/titanium bimetal doped carbon material on the graphite felt to obtain the amidoxime-modified iron/titanium bimetal doped carbon electrode.
  2. 2. The preparation method of the amidoxime-modified iron/titanium bimetal-doped carbon electrode according to claim 1, wherein the mass volume ratio of the 2-amino terephthalic acid, the N, N-dimethylformamide, the methanol and the tetrabutyl titanate in S1 is 0.1-1g:1-20mL:1-20mL:0.1-20mL, and the volume ratio of the acetic acid to the methanol is 0.01-1:1-20; The temperature of the heat treatment is 50-240 ℃, and the time of the heat treatment is 6-72h.
  3. 3. The method for preparing the amidoxime-modified iron/titanium bimetal-doped carbon electrode according to claim 1, wherein the mass-volume ratio of the ferrous acetate, the 1, 10-phenanthroline, the ethanol and the water in the S2 is 0.0050-1g:0.0200-1g:1-20mL:1-20mL.
  4. 4. The method for preparing an amidoxime-modified iron/titanium bimetal doped carbon electrode according to claim 1, wherein the mass-to-volume ratio of Ti-MOF to water in S3 is 0.01-1g:1-20mL, and the mass-to-volume ratio of Ti-MOF to composite solution is 0.01-1g:1-20mL; the reaction temperature is 20-100 ℃, and the reaction time is 1-12h.
  5. 5. The method for preparing an amidoxime-modified iron/titanium bimetal-doped carbon electrode according to claim 1, wherein the temperature of the carbonization-reduction reaction in S4 is 500-1000 ℃ and the time of the carbonization-reduction reaction is 0.1-2h; the temperature of the nitriding reaction is 500-1000 ℃, and the time of the nitriding reaction is 0.1-2h.
  6. 6. The method for preparing the amidoxime-modified iron/titanium bimetal-doped carbon electrode according to claim 1, wherein the mass-volume ratio of Fe/TiO x /C, polyacrylonitrile, azobisisobutyronitrile and N, N-dimethylformamide in S5 is 25-35mg:10-25mg:0.3-0.8mg:25mL, the temperature of the oil bath is 115-125 ℃, and the time of the oil bath is 1-3h; The mass volume ratio of Fe/TiO x /C, water, hydroxylamine hydrochloride and sodium carbonate is 25-35mg:30mL:45-55mg:70-80mg; the temperature of the amidoxime reaction is 65-75 ℃, and the time of the amidoxime reaction is 10-14h.
  7. 7. An amidoxime-modified iron/titanium bimetal-doped carbon electrode prepared by the method for preparing an amidoxime-modified iron/titanium bimetal-doped carbon electrode of any one of claims 1 to 6.
  8. 8. Use of an amidoxime-modified iron/titanium bi-metal doped carbon electrode according to claim 7 for electrochemical uranium extraction from seawater.
  9. 9. The method for using the amidoxime-modified iron/titanium bi-metal doped carbon electrode in electrochemical uranium extraction from seawater according to claim 8, comprising the following steps: (1) Assembling the cathode and the anode in a penetrating type electrolytic cell by taking the amidoxime-modified iron/titanium bimetal-doped carbon electrode as a cathode and a platinum sheet as an anode; (2) After the pH value of the seawater is regulated to 2-7, the seawater is introduced into a penetrating type electrolytic tank, the seawater flows through a cathode and then flows through an anode and flows out of the electrolytic tank, the input constant voltage of the cathode and the anode is controlled to be minus 5 to minus 0.5V, and electrochemical seawater uranium extraction is carried out.
  10. 10. The method for using an amidoxime-modified iron/titanium bimetal doped carbon electrode in electrochemical uranium extraction from seawater according to claim 9, wherein the flow rate of the inlet in the step (2) is 1-150mL/min.

Description

Amidoxime modified iron/titanium bimetal doped carbon electrode and preparation method and application thereof Technical Field The invention relates to the technical field of electrochemical uranium extraction, in particular to an amidoxime-modified iron/titanium bimetal doped carbon electrode, and a preparation method and application thereof. Background The nuclear energy is clean and efficient green energy, and development of the nuclear energy is beneficial to pushing the energy structure to transform. Uranium is the main fuel of the nuclear energy industry, and the uranium content in seawater is about 1000 times of the total reserves of land uranium ores, so that the uranium is expected to provide abundant raw materials for the nuclear energy industry. At present, the adsorption method is a mainstream technology for extracting uranium from seawater, but the adsorption method has technical bottlenecks of low efficiency, low speed and the like in the technology for extracting uranium from seawater due to low concentration of uranium in seawater, more competitive ions, serious biofouling and the like. The electrochemical uranium extraction technology can utilize an electric field to accelerate the migration and enrichment of uranyl ions in seawater to electrode materials, and further convert the uranyl ions into solid sediments through electrochemical reaction, so that the collection and purification of products are facilitated. However, the current electrochemical seawater uranium extraction technology depends on high operation voltage above-3V, which not only results in high energy consumption cost, but also is easy to cause side reactions, and the main reasons are that 1) high-performance electrode materials are lacked, high reaction potential energy needs to be overcome for uranium deposition, 2) mass transfer efficiency of a reaction system is low, and the difficulty of uranyl ions contacting the surface of an electrode is high. In addition, a large amount of Na + existing in the seawater is easy to be co-deposited and separated out with uranium in the form of Na xUyOz, and the purity of uranium products is affected. Disclosure of Invention The invention aims to provide an amidoxime-modified iron/titanium bimetal doped carbon electrode, a preparation method and application thereof, wherein the electrode has a porous structure, is favorable for adsorbing uranyl ions, and has strong catalytic activity of Fe and Ti bimetal sites and can promote the electrodeposition efficiency of uranium. In order to achieve the above object, the present invention provides a method for preparing an amidoxime-modified iron/titanium bimetal doped carbon electrode, comprising the steps of: s1, mixing 2-amino terephthalic acid, N-dimethylformamide, methanol and tetrabutyl titanate, performing ultrasonic treatment to obtain a suspension, and adding acetic acid into the suspension for heat treatment to obtain Ti-MOF; S2, mixing ferrous acetate, 1, 10-phenanthroline, ethanol and water to obtain a composite solution; s3, mixing the Ti-MOF with water to obtain a Ti-MOF solution, and placing the Ti-MOF solution into a composite solution for reaction to obtain an intermediate product; S4, performing carbonization reduction reaction on the intermediate product in an argon atmosphere, then performing nitridation reaction in an ammonia atmosphere, and cooling to obtain Fe/TiO x/C; S5, mixing Fe/TiO x/C, polyacrylonitrile, azodiisobutyronitrile and N, N-dimethylformamide, carrying out oil bath, dispersing an oil bath product in water, adding hydroxylamine hydrochloride and sodium carbonate, and carrying out amidoxime reaction to obtain an amidoxime modified iron/titanium bimetal doped carbon material; S6, coating the amidoxime-modified iron/titanium bimetal doped carbon material on the graphite felt to obtain the amidoxime-modified iron/titanium bimetal doped carbon electrode. In the invention, the specific process of mixing in S1 comprises the steps of adding 2-amino terephthalic acid, N-dimethylformamide and methanol into a beaker, stirring for 12-18min at a stirring rate of 600-700rpm at a temperature of 18-30 ℃, then adding tetrabutyl titanate, and carrying out ultrasonic treatment for 10-20min to obtain a suspension. In the present invention, the mass-volume ratio of the 2-aminoterephthalic acid, the N, N-dimethylformamide, the methanol and the tetrabutyltitanate in S1 is preferably 0.1-1g:1-20mL:1-20mL, more preferably 0.3-0.6g:8-15mL:1-1.2mL:0.2-0.4mL, further preferably 0.54g:9mL:1.1mL:0.26mL, the volume ratio of the acetic acid to the methanol is preferably 0.01-1:1-20, more preferably 0.01-0.02:1-1.2, further preferably 0.015:1.1, the temperature of the heat treatment is preferably 50-240 ℃, more preferably 100-200 ℃, further preferably 150 ℃, and the time of the heat treatment is preferably 6-72h, more preferably 10-20h, further preferably 15h. In the invention, after the heat treatment in S1 is finished, the product obtaine