CN114014413A - Modified graphene electrode material with function of adsorbing and electrically reducing radionuclide - Google Patents

Modified graphene electrode material with function of adsorbing and electrically reducing radionuclide Download PDF

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Publication number
CN114014413A
CN114014413A CN202111431259.8A CN202111431259A CN114014413A CN 114014413 A CN114014413 A CN 114014413A CN 202111431259 A CN202111431259 A CN 202111431259A CN 114014413 A CN114014413 A CN 114014413A
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substance
mixed solution
electrode material
solution
adsorbing
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邵可欣
豆俊峰
郭彦青
滕彦国
丁爱中
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Beijing Normal University
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Beijing Normal University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4676Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691Capacitive deionisation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46133Electrodes characterised by the material

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Electrochemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a modified graphene electrode material with a function of adsorbing electroreduction radionuclide. Adding graphene and acrylonitrile into deionized water, and stirring and standing to obtain a suspension B; heating the suspension B, and adding persulfuric acid for reaction to obtain a mixed solution C; centrifugally separating and cleaning the mixed solution C, and removing supernatant to obtain a substance F; preparing a hydroxylamine solution I, adding the substance F into the hydroxylamine solution I, stirring, carrying out centrifugal separation, cleaning and drying to obtain the modified graphene electrode material. The invention has the advantages that the preparation process of the electrode material is simple, and the treatment effect is good when the electrode material is used for the electroreduction repair of the radionuclide.

Description

Modified graphene electrode material with function of adsorbing and electrically reducing radionuclide
Technical Field
The invention belongs to the technical field of in-situ electrochemical restoration and treatment of radionuclide underground water pollution, and particularly relates to a modified graphene electrode material with a function of adsorbing and electrically reducing radionuclides.
Background
The radioactive polluted groundwater remediation is an extremely complicated worldwide problem, and a large amount of radioactive wastewater is generated in the nuclear fuel circulation process of uranium ore exploitation, nuclear fuel processing and the like. In the uranium mining and metallurgy production process, the produced uranium-containing wastewater has certain threat to human health and ecological environment, and the effective treatment of radioactive pollution underground water is the current hotspot problem. In addition, for the possible uranium resource shortage phenomenon in the future, the material and the technology for separating and recovering uranium from the non-traditional environmental water body or seawater play an important role in fully utilizing the uranium resource. Compared with methods such as a chemical precipitation method, an ion exchange method, a solvent extraction method, filtration and a reverse osmosis method, the adsorption method has the characteristics of low cost, strong adsorption capacity, excellent selectivity and the like. Carbon materials are now widely used as adsorbent materials for adsorbing carbon materials such as u (vi), carbon nanotubes, activated carbon, and graphite. Graphene is a research hotspot in recent years, and the surface of graphene has a large number of gaps and folds, so that the graphene has a large specific surface area and is beneficial to adsorption of other substances; the Graphene Oxide (GO) is an oxide of graphene, not only has the advantage of large specific surface area, but also has a large number of oxygen-containing functional groups on the surface, so that the adsorption performance is stronger, and therefore, the research on the adsorption performance of the radionuclide on the graphene oxide is of great significance. Graphene Oxide (GO) is a good adsorption material and can be used for adsorbing various heavy metal ions. The oxygen-containing functional groups on the surface of GO enable the GO to have better hydrophilicity, but are easy to agglomerate, so that the recycling of GO is limited. Therefore, in order to improve the adsorption performance and separation effect of graphene oxide on heavy metal ions, graphene oxide can be modified by methods such as amination, acylchlorination, hydroformylation or polymer modification. Polyacrylonitrile (PAN) is a common film-forming and fiber-forming material, and is widely used for film preparation due to its advantages of mold resistance, corrosion resistance, chemical stability, biocompatibility, and the like. The amidoxime group has very good adsorption capacity to heavy metal ions, particularly uranium ions. At present, a modified graphene electrode material with the function of adsorbing electrically reduced radionuclides is still lacked, and the uranium removal efficiency of the electrode material is improved by modifying the oxidized graphene with amidoxime groups.
Disclosure of Invention
The invention aims to provide a modified graphene electrode material with a function of adsorbing and electrically reducing radionuclides, which is prepared by the following specific steps:
(1) adding 1mL of acrylonitrile into 300mL of deionized water to obtain a mixed solution A;
(2) adding 0.2g of graphene into the mixed solution A, stirring for 20 minutes at room temperature, and then standing for 8 hours to obtain a suspension B;
(3) putting the suspension B into a constant-temperature water bath, heating to 50 ℃, adding 100mL of persulfuric acid with the molar concentration of 0.1M, and reacting for 3 hours to obtain a mixed solution C;
(4) carrying out centrifugal separation on the compound in the mixed solution C, and removing supernatant to obtain a substance D;
(5) cleaning the substance D with a solution with the volume ratio of methanol to water being 5:1 for 4 times, and removing redundant ammonium persulfate and acrylonitrile monomers to obtain a substance E;
(6) washing the substance E with deionized water for 4 times to obtain a substance F;
(7) adding 140.0G of hydroxylamine hydrochloride into 800mL of a solution of methanol and water in a volume ratio of 5:1 to obtain a mixed solution G;
(8) regulating the pH of the mixed solution G by using a NaOH solution with the molar concentration of 2M until the pH is 10 to obtain a mixed solution H;
(9) filtering the mixed solution H, and removing NaCl precipitates to obtain a mixed solution I;
(10) adding the substance F into 100mL of the mixed solution I to obtain a mixed solution J;
(11) placing the mixed solution J into a constant-temperature water bath kettle at the temperature of 70 ℃, and stirring for reacting for 3 hours to obtain a mixed solution K;
(12) carrying out centrifugal separation on the mixed solution K, and removing supernatant to obtain a substance L;
(13) washing the substance L with a solution of methanol and water at a volume ratio of 5:1 for 4 times to obtain a substance M;
(14) washing the substance M with deionized water for 4 times to obtain a substance N;
(15) and drying the substance N for 5 hours at the temperature of 60 ℃ to obtain the substance, namely the modified graphene electrode material with the function of adsorbing the electroreduction radionuclide.
The invention has the advantages that the preparation process of the electrode material is simple, and the treatment effect is good when the electrode material is used for the electroreduction repair of the radionuclide.
Detailed Description
The invention provides a modified graphene electrode material with a function of adsorbing and electrically reducing radionuclides, and the implementation process is described by an example.
Example 1.
The preparation method of the modified graphene electrode material with the function of adsorbing the electroreduction radionuclide comprises the following specific steps:
(1) adding 1mL of acrylonitrile into 300mL of deionized water to obtain a mixed solution A;
(2) adding 0.2g of graphene into the mixed solution A, stirring for 20 minutes at room temperature, and then standing for 8 hours to obtain a suspension B;
(3) putting the suspension B into a constant-temperature water bath, heating to 50 ℃, adding 100mL of persulfuric acid with the molar concentration of 0.1M, and reacting for 3 hours to obtain a mixed solution C;
(4) carrying out centrifugal separation on the compound in the mixed solution C, and removing supernatant to obtain a substance D;
(5) cleaning the substance D with a solution with the volume ratio of methanol to water being 5:1 for 4 times, and removing redundant ammonium persulfate and acrylonitrile monomers to obtain a substance E;
(6) washing the substance E with deionized water for 4 times to obtain a substance F;
(7) adding 140.0G of hydroxylamine hydrochloride into 800mL of a solution of methanol and water in a volume ratio of 5:1 to obtain a mixed solution G;
(8) regulating the pH of the mixed solution G by using a NaOH solution with the molar concentration of 2M until the pH is 10 to obtain a mixed solution H;
(9) filtering the mixed solution H, and removing NaCl precipitates to obtain a mixed solution I;
(10) adding the substance F into 100mL of the mixed solution I to obtain a mixed solution J;
(11) placing the mixed solution J into a constant-temperature water bath kettle at the temperature of 70 ℃, and stirring for reacting for 3 hours to obtain a mixed solution K;
(12) carrying out centrifugal separation on the mixed solution K, and removing supernatant to obtain a substance L;
(13) washing the substance L with a solution of methanol and water at a volume ratio of 5:1 for 4 times to obtain a substance M;
(14) washing the substance M with deionized water for 4 times to obtain a substance N;
(15) and drying the substance N for 5 hours at the temperature of 60 ℃ to obtain the substance, namely the modified graphene electrode material with the function of adsorbing the electroreduction radionuclide.
The application of the modified graphene electrode material with the function of adsorbing the electroreduction radionuclide:
(1) the prepared electrode material was dispersed in deionized water at a concentration of 1.0mg mL-1Then, ultrasonic treatment is carried out for 60min to ensure that the mixture is uniformly dispersed. Immersing a small square carbon felt cut into 2cm multiplied by 2cm into the solution, stirring for 60min to ensure that the carbon felt is uniformly immersed, and then drying at room temperature to obtain a modified carbon felt electrode;
(2) under the condition that the initial uranium solution concentration is 30mg/L, the direct current voltage stabilization is set to be 5V, and the electrolyte Na2SO4The concentration is 5g/L, the graphite rod is used as an anode, the modified carbon felt electrode is used as a cathode, the electrodeposition reaction is carried out for 30min, and the uranium removal rate can reach 78.94%.

Claims (1)

1. The modified graphene electrode material with the function of adsorbing and electrically reducing radionuclides is characterized by comprising the following steps of:
(1) adding 1mL of acrylonitrile into 300mL of deionized water to obtain a mixed solution A;
(2) adding 0.2g of graphene into the mixed solution A, stirring for 20 minutes at room temperature, and then standing for 8 hours to obtain a suspension B;
(3) putting the suspension B into a constant-temperature water bath, heating to 50 ℃, adding 100mL of persulfuric acid with the molar concentration of 0.1M, and reacting for 3 hours to obtain a mixed solution C;
(4) carrying out centrifugal separation on the compound in the mixed solution C, and removing supernatant to obtain a substance D;
(5) cleaning the substance D with a solution with the volume ratio of methanol to water being 5:1 for 4 times, and removing redundant ammonium persulfate and acrylonitrile monomers to obtain a substance E;
(6) washing the substance E with deionized water for 4 times to obtain a substance F;
(7) adding 140.0G of hydroxylamine hydrochloride into 800mL of a solution of methanol and water in a volume ratio of 5:1 to obtain a mixed solution G;
(8) regulating the pH of the mixed solution G by using a NaOH solution with the molar concentration of 2M until the pH is 10 to obtain a mixed solution H;
(9) filtering the mixed solution H, and removing NaCl precipitates to obtain a mixed solution I;
(10) adding the substance F into 100mL of the mixed solution I to obtain a mixed solution J;
(11) placing the mixed solution J into a constant-temperature water bath kettle at the temperature of 70 ℃, and stirring for reacting for 3 hours to obtain a mixed solution K;
(12) carrying out centrifugal separation on the mixed solution K, and removing supernatant to obtain a substance L;
(13) washing the substance L with a solution of methanol and water at a volume ratio of 5:1 for 4 times to obtain a substance M;
(14) washing the substance M with deionized water for 4 times to obtain a substance N;
(15) and drying the substance N for 5 hours at the temperature of 60 ℃ to obtain the substance, namely the modified graphene electrode material with the function of adsorbing the electroreduction radionuclide.
CN202111431259.8A 2021-11-29 2021-11-29 Modified graphene electrode material with function of adsorbing and electrically reducing radionuclide Pending CN114014413A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109477159A (en) * 2016-06-30 2019-03-15 小利兰·斯坦福大学托管委员会 For extraction/removal metal ion electrochemical deposition from water
CN110449141A (en) * 2019-09-10 2019-11-15 江苏中科睿赛环境工程有限公司 A kind of preparation method of polyacrylonitrile fibre organic waste-gas adsorbant, adsorbent equipment and adsorption method using it
CN111484644A (en) * 2020-04-17 2020-08-04 东华理工大学 Method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel
CN111518248A (en) * 2020-04-29 2020-08-11 西南科技大学 Amidoxime group modified graphene oxide material and preparation method thereof
CN112547026A (en) * 2020-10-28 2021-03-26 海南大学 Uranium adsorption material, preparation method thereof and application of uranium adsorption material in adsorption recovery of uranium in seawater

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109477159A (en) * 2016-06-30 2019-03-15 小利兰·斯坦福大学托管委员会 For extraction/removal metal ion electrochemical deposition from water
CN110449141A (en) * 2019-09-10 2019-11-15 江苏中科睿赛环境工程有限公司 A kind of preparation method of polyacrylonitrile fibre organic waste-gas adsorbant, adsorbent equipment and adsorption method using it
CN111484644A (en) * 2020-04-17 2020-08-04 东华理工大学 Method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel
CN111518248A (en) * 2020-04-29 2020-08-11 西南科技大学 Amidoxime group modified graphene oxide material and preparation method thereof
CN112547026A (en) * 2020-10-28 2021-03-26 海南大学 Uranium adsorption material, preparation method thereof and application of uranium adsorption material in adsorption recovery of uranium in seawater

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Application publication date: 20220208