CN112246243A - Preparation method of hydrophilic graphene/spinel type ferrite composite material - Google Patents

Preparation method of hydrophilic graphene/spinel type ferrite composite material Download PDF

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CN112246243A
CN112246243A CN202011135091.1A CN202011135091A CN112246243A CN 112246243 A CN112246243 A CN 112246243A CN 202011135091 A CN202011135091 A CN 202011135091A CN 112246243 A CN112246243 A CN 112246243A
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composite material
graphene
type ferrite
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spinel type
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胥焕岩
李博
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Harbin University of Science and Technology
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Harbin University of Science and Technology
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Abstract

The invention relates to the functionalization of graphene and the in-situ assembly preparation of a composite material, belonging to the field of inorganic non-metallic materials. The method can continuously realize the functionalization of the graphene oxide, the in-situ loading of the spinel type ferrite crystal grains and the in-situ reduction of the functionalized graphene oxide, and prepare the graphene/spinel type ferrite composite material with excellent hydrophilic performance, and has the advantages of easily obtained raw materials, simple process and convenient operation. The method comprises the following specific steps: adjusting the pH value of the graphene oxide aqueous solution to be acidic, adding a modifier, performing ultrasonic dispersion, and then keeping the temperature at 60 ℃ for 1-4 hours; adjusting the pH value of the obtained mixed solution to be neutral, adding an iron-containing reagent, performing ultrasonic dispersion again, keeping the temperature at 85-95 ℃, dropwise adding a precipitator to form a crystallized product, and continuing to keep the temperature for 3-5 hours after dropwise adding is finished; after magnetic separation, the crystallized product was washed repeatedly with a specific solvent and dried at 60 ℃ for 12 hours. The graphene/spinel type ferrite composite material prepared by the method has a water contact angle of only 15.02 degrees and shows excellent hydrophilicity.

Description

Preparation method of hydrophilic graphene/spinel type ferrite composite material
Technical Field
The invention relates to the functionalization of graphene and the in-situ assembly preparation of a composite material, belonging to the field of inorganic non-metallic materials.
Background
In the past two decades, the modern industry is rapidly developed, agricultural chemicals and various nursing products are widely applied, and the hard-to-degrade pollutants such as endocrine disruptors, halogenated aliphatic compounds, aromatic compounds and the like in the water body are widely existed and accumulated. Advanced oxidation technologies (AOPs) based on heterogeneous reactions are a promising technology for wastewater recovery. For this reason, the development of new efficient and environmentally friendly heterogeneous catalysts is a hot issue in the research of AOPs.
Spinel type ferrite is an ionic compound with a general formula of AB2O4. A and B are usually transition metal elements, A2 +The ions occupy octahedral voids, B3+Half of the ions occupy tetrahedral voids and the other half occupy octahedral voids. Spinel ferrites can complete redox cycling on their own due to their specific structure and valence ratio. Compared with homogeneous ionic reaction, the rate of heterogeneous redox reaction based on spinel type ferrite is greatly improved. The method has research value and practical significance when being applied to the advanced oxidation technology. However, it is a limited study to improve the performance of spinel ferrite only by adjusting the element species and the grain size. Graphene, as a two-dimensional material, has excellent physicochemical properties such as high carrier mobility and an outstanding specific surface area. If the spinel ferrite is loaded on the surface of the graphene, the potential value of the functional composite material in the field of environmental engineering is undoubtedly improved due to the synergistic effect generated between the spinel ferrite and the graphene. However, due to the sub-magnetic property of part of spinel type ferrite and the hydrophobic property of graphene, the composite material is easy to aggregate during the heterogeneous catalysis reaction, the dispersion stability is lost, and the activity is reduced. Therefore, functionalizing graphene to enhance the hydrophilicity is an effective method for overcoming the above disadvantages. Currently, there are numerous methods of graphene functionalization, such as pi-pi bond, hydrogen bonding, noncovalent bond functionalization by ionic bond interaction, and covalent bond functionalization of the carbon backbone. If the method is adopted to functionalize the graphene independently, the process steps and the operation difficulty of the whole preparation process are increased, which is contrary to the resource conservation and environmental friendlinessGood development concept.
The innovative idea of the invention is to develop a liquid phase preparation process with simple process and controllable operation by taking graphene oxide and readily available chemical reagents as raw materials, and continuously realize the functionalization of graphene oxide, the in-situ loading of spinel-type ferrite and the in-situ reduction of functionalized graphene oxide. The method does not need to separate intermediate, and can save economy and resources to a greater extent. Researches show that the hydrophilic graphene/spinel ferrite composite material prepared by the method has a small water contact angle and can be uniformly dispersed in an aqueous solution for more than 30 min. In addition, the composite material prepared by the method catalyzes a heterogeneous Fenton reaction, so that the methyl orange dye (20mg/L) can be degraded by 100% within 60 min.
Disclosure of Invention
The basic idea of the preparation method of the hydrophilic graphene/spinel-type ferrite composite material provided by the invention is that rich oxygen-containing groups on the surface of graphene oxide are grafted with an organic modifier, and then electronegativity on the surface of graphene oxide is used for preferentially adsorbing metal cations in the spinel-type ferrite, so that in-situ loading of spinel-type ferrite nano-crystalline grains on the surface of graphene oxide is realized. Meanwhile, the in-situ reduction of the functionalized graphene oxide is synchronously completed through the control of experimental conditions.
The preparation method of the hydrophilic graphene/spinel type ferrite composite material provided by the invention has the following main technical scheme:
1) adjusting the pH value of the graphene oxide aqueous solution to be acidic, adding a certain mass of modifier, performing ultrasonic dispersion, and then keeping the temperature at 60 ℃ for 1-4 hours;
2) adjusting the pH value of the mixed solution obtained in the step 1) to be neutral, adding a certain mass of iron-containing reagent, performing ultrasonic dispersion, keeping the temperature at 85-95 ℃, dropwise adding a precipitator to form a crystallized product, and keeping the temperature for 3-5 hours after dropwise adding is finished;
3) and (3) carrying out solid-liquid separation on the crystallized product obtained in the step 2) by using a magnet, repeatedly washing the crystallized product by using a solvent, and drying the washed product for 12 hours at the temperature of 60 ℃ to obtain the hydrophilic graphene/spinel type ferrite composite material.
In the technical scheme of the invention, the modifier used in the step 1) is one or a combination of more of sulfanilic acid, 4-hydroxy sodium benzenesulfonate, sodium hexadecylsulfonate and sodium dodecyl benzenesulfonate.
In the technical scheme of the invention, the iron-containing reagent used in the step 2) is FeSO4·7H2O、FeCl2·4H2O、FeCl3·6H2O、Fe(NO3)2·9H2O、Fe(NO3)3One or more of NaOH and NaNO as precipitant3、KOH、KNO3、MnCl2·4H2O、Mn(NO3)2、ZnSO4·H2O、ZnCl2、Zn(NO3)2、CuSO4、Cu(NO3)2·6H2O、CuCl2·2H2O、MgCl2·6H2O、Mg(NO3)2、Co(NO3)2·6H2O、CoCl2·6H2O、NiCl2·6H2O or a combination of several O.
In the technical scheme of the invention, the washing solvent used in the step 3) is one or more of deionized water, absolute ethyl alcohol, acetone, ethylene glycol, styrene, perchloroethylene, trichloroethylene, dichloroethylene, triethanolamine, xylene, methanol, isopropanol, methyl acetate, ethyl acetate, propyl acetate, methyl butanone and N, N-dimethylformamide.
The invention provides a preparation method of a hydrophilic graphene/spinel type ferrite composite material, wherein the spinel type ferrite comprises zinc ferrite (ZnFe)2O4) Copper ferrite (CuFe)2O4) Magnesium ferrite (MgFe)2O4) Cobalt ferrite (CoFe)2O4) Manganese ferrite (MnFe)2O4) Nickel ferrite (NiFe)2O4) Ferroferric oxide (Fe)3O4) And solid solutions thereof.
The method provided by the invention continuously realizes the functionalization of the graphene oxide, the loading of the spinel crystal grains and the in-situ reduction of the functionalized graphene oxide. The graphene oxide is self-made by the research room, and other reagents are analytically pure. The method provided by the invention is simple to operate, easy to control, low in synthesis temperature, low in energy consumption, low in preparation cost, green and environment-friendly in used reagent, non-toxic, non-corrosive and capable of realizing batch production.
Drawings
Fig. 1 is a water contact angle test result of a representative sample of a hydrophilic graphene/spinel ferrite composite material.
Fig. 2 is a photograph of the dispersibility in water of a representative sample of a hydrophilic graphene/spinel ferrite composite.
Detailed Description
Example 1
Adjusting the pH value of the graphene oxide aqueous solution to acidity by using 5% dilute hydrochloric acid, adding a certain mass of sodium hexadecylsulfonate, then placing the mixture in a constant-temperature water bath at 60 ℃, mechanically stirring the mixture, and reacting the mixture for 2 hours. After the reaction is finished, 1mol/L NaOH solution is used for adjusting the pH value of the product to be neutral, and FeCl with certain mass is added according to the stoichiometric ratio3·6H2O and FeCl2·4H2And O. Placing the mixed solution in a constant-temperature water bath kettle, reacting at 95 ℃, continuously stirring, and dropwise adding 2mol/L NaOH and MnCl in the reaction process2·4H2The total volume of O mixed solution is 80mL, and the reaction is continued after the dropwise addition is finished, wherein the total reaction time is 5 hours. After the reaction is finished, repeatedly washing the mixture for three times by using acetone and methyl acetate, and drying the mixture for 12 hours at the temperature of 60 ℃.
Example 2
Adjusting the pH value of the graphene oxide aqueous solution to acidity by using 5% dilute hydrochloric acid, adding a certain mass of 4-hydroxy benzene sodium sulfonate and sulfanilic acid, then placing in a constant-temperature water bath at 60 ℃, mechanically stirring, and reacting for 1 hour. After the reaction is finished, 1mol/L NaOH solution is used for adjusting the pH value of the product to be neutral, and certain mass of Fe (NO) and Fe (NO) are added according to the stoichiometric ratio3)2·9H2And O. Placing the mixed solution in a constant-temperature water bath kettle, reacting at 90 ℃, continuously stirring, and dropwise adding 2mol/L KOH and KNO in the reaction process3、Co(NO3)2·6H2O mixed liquid80mL, and the reaction was continued after the addition was completed, with a total reaction time of 4 hours. After the reaction is finished, repeatedly washing the mixture for three times by using methanol and isopropanol, and drying the mixture for 12 hours at the temperature of 60 ℃.
Example 3
Adjusting the pH value of the graphene oxide aqueous solution to acidity by using 5% dilute hydrochloric acid, adding a certain mass of sodium dodecyl benzene sulfonate, then placing the mixture in a constant-temperature water bath at 60 ℃, mechanically stirring the mixture, and reacting for 2 hours. After the reaction is finished, 1mol/L NaOH solution is used for adjusting the pH value of the product to be neutral, and certain mass of FeSO is added according to the stoichiometric ratio4·7H2And O. Placing the mixed solution in a constant-temperature water bath kettle, reacting at 95 ℃, continuously stirring, and dropwise adding 2mol/L NaOH and NaNO in the reaction process3The total volume of the mixed solution was 80mL, and the reaction was continued after the addition of the solution was completed, with the total reaction time being 4 hours. After the reaction is finished, repeatedly washing the mixture with deionized water for three times, and drying the mixture for 12 hours at the temperature of 60 ℃.
Example 4
Adjusting the pH value of the graphene oxide aqueous solution to acidity by using 5% dilute hydrochloric acid, adding certain mass of sulfanilic acid, then placing in a constant-temperature water bath at 60 ℃, mechanically stirring, and reacting for 4 hours. After the reaction is finished, 1mol/L NaOH solution is used for adjusting the pH value of the product to be neutral, and certain mass of FeSO is added according to the stoichiometric ratio4·7H2And O. Putting the mixed solution into a constant-temperature water bath kettle, reacting at 90 ℃, continuously stirring, and dropwise adding 4mol/L NaOH and Cu (NO) into the mixed solution in the reaction process3)2·6H2The total volume of O mixed solution is 80mL, and the reaction is continued after the dropwise addition is finished, wherein the total reaction time is 3 hours. After the reaction is finished, the mixture is repeatedly washed three times by using glycol and styrene and dried for 12 hours at the temperature of 60 ℃.
Example 5
Adjusting the pH value of the graphene oxide aqueous solution to acidity by using 5% dilute hydrochloric acid, adding a certain mass of sodium hexadecylsulfonate, then placing the mixture in a constant-temperature water bath at 60 ℃, mechanically stirring the mixture, and reacting the mixture for 1 hour. After the reaction is finished, 1mol/L NaOH solution is used for adjusting the pH value of the product to be neutral, and a certain mass of Fe (NO) is added according to the stoichiometric ratio3)2·9H2And O. Placing the mixed solution in a constant-temperature water bathReacting at 90 deg.C in a pot, stirring, and dripping 2mol/L ZnSO dropwise during the reaction4·H2O, NaOH and Na2SO4The total volume of the mixed solution was 80mL, and the reaction was continued after the addition of the solution was completed, with the total reaction time being 5 hours. After the reaction is finished, the mixture is repeatedly washed three times by propyl acetate and methyl butanone and dried for 12 hours at the temperature of 60 ℃.
Example 6
Adjusting the pH value of the graphene oxide aqueous solution to acidity by using 5% dilute hydrochloric acid, adding a certain mass of sodium dodecyl benzene sulfonate, then placing the mixture in a constant-temperature water bath at 60 ℃, mechanically stirring the mixture, and reacting the mixture for 3 hours. After the reaction is finished, 1mol/L NaOH solution is used for adjusting the pH value of the product to be neutral, and certain mass of FeSO is added according to the stoichiometric ratio4·7H2O and FeCl2·4H2And O. Placing the mixed solution in a constant temperature water bath kettle, reacting at 90 deg.C while stirring, and dropwise adding 1mol/L NaOH and Co (NO) into the mixed solution3)2·6H2The total volume of O mixed solution is 80mL, and the reaction is continued after the dropwise addition is finished, wherein the total reaction time is 4 hours. After the reaction was completed, the reaction mixture was washed with N, N-dimethylformamide repeatedly three times and dried at 60 ℃ for 12 hours.
Example 7
Adjusting the pH value of the graphene oxide aqueous solution to acidity by using 5% dilute hydrochloric acid, adding a certain mass of sodium benzenesulfonate, then placing the mixture in a constant-temperature water bath at 60 ℃, mechanically stirring, and reacting for 4 hours. After the reaction is finished, 1mol/L NaOH solution is used for adjusting the pH value of the product to be neutral, and FeCl with certain mass is added according to the stoichiometric ratio3·6H2O and Fe (NO)3)2·9H2And O. Placing the mixed solution in a constant-temperature water bath kettle, reacting at 95 ℃, continuously stirring, and dropwise adding 5mol/L KOH and NiCl in the reaction process2·6H2The total volume of O mixed solution is 80mL, and the reaction is continued after the dropwise addition is finished, wherein the total reaction time is 4 hours. After the reaction is finished, washing the reaction product by using dichloroethylene and triethanolamine repeatedly for three times, and drying the reaction product for 12 hours at the temperature of 60 ℃.

Claims (5)

1. The invention aims to develop a preparation method of a hydrophilic graphene/spinel type ferrite composite material with simple process and easy control so as to obtain a new heterogeneous Fenton catalytic composite material with high catalytic activity and magnetic separation recovery, and is characterized by comprising the following process steps:
1) adjusting the pH value of the graphene oxide aqueous solution to be acidic, adding a certain mass of modifier, performing ultrasonic dispersion, and then keeping the temperature at 60 ℃ for 1-4 hours;
2) adjusting the pH value of the mixed solution obtained in the step 1) to be neutral, adding a certain mass of iron-containing reagent, performing ultrasonic dispersion, keeping the temperature at 85-95 ℃, dropwise adding a precipitator to form a crystallized product, and keeping the temperature for 3-5 hours after dropwise adding is finished;
3) and (3) carrying out solid-liquid separation on the crystallized product obtained in the step 2) by using a magnet, repeatedly washing the crystallized product by using a solvent, and drying the washed product for 12 hours at the temperature of 60 ℃ to obtain the hydrophilic graphene/spinel type ferrite composite material.
2. The method of claim 1, wherein the spinel-type ferrite material comprises zinc ferrite (ZnFe)2O4) Copper ferrite (CuFe)2O4) Magnesium ferrite (MgFe)2O4) Cobalt ferrite (CoFe)2O4) Manganese ferrite (MnFe)2O4) Nickel ferrite (NiFe)2O4) Ferroferric oxide (Fe)3O4) And solid solutions thereof.
3. The preparation method of the hydrophilic graphene/spinel type ferrite composite material according to claim 1, wherein the modifier used in the step 1) is one or a combination of more of sulfanilic acid, 4-hydroxy benzene sulfonic acid sodium salt, hexadecyl sodium salt and dodecyl benzene sulfonic acid sodium salt.
4. The method for preparing the hydrophilic graphene/spinel type ferrite composite material according to claim 1, wherein the iron-containing reagent used in the step 2) is FeSO4·7H2O、FeCl2·4H2O、FeCl3·6H2O、Fe(NO3)2·9H2O、Fe(NO3)3One or more of NaOH and NaNO as precipitant3、KOH、KNO3、MnCl2· 4H2O、Mn(NO3)2、ZnSO4·H2O、ZnCl2、Zn(NO3)2、CuSO4、Cu(NO3)2·6H2O、CuCl2·2H2O、MgCl2·6H2O、Mg(NO3)2、Co(NO3)2·6H2O、CoCl2·6H2O、NiCl2·6H2O or a combination of several O.
5. The preparation method of the hydrophilic graphene/spinel type ferrite composite material according to claim 1, wherein the washing solvent used in the step 3) is one or more of deionized water, absolute ethyl alcohol, acetone, ethylene glycol, styrene, perchloroethylene, trichloroethylene, dichloroethylene, triethanolamine, xylene, methanol, isopropanol, methyl acetate, ethyl acetate, propyl acetate, methyl butanone and N, N-dimethylformamide.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN115254025A (en) * 2022-08-19 2022-11-01 常州大学 Preparation method of printing and dyeing sludge dehydrating agent and method for conditioning printing and dyeing sludge by using printing and dyeing sludge dehydrating agent

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101941842A (en) * 2010-10-11 2011-01-12 东华大学 Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material
CN103030208A (en) * 2013-01-08 2013-04-10 哈尔滨工业大学 Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters
CN103341346A (en) * 2013-06-26 2013-10-09 江苏省环境科学研究院 Preparation method of manganese ferrite nanoparticle-graphene compound
CN105478078A (en) * 2015-11-25 2016-04-13 蚌埠学院 Preparation method and use of highly dispersed magnetic graphene nanometer adsorbent
CN106475100A (en) * 2016-08-30 2017-03-08 江苏金茂源生物化工有限责任公司 The preparation method and application of Graphene/ferroferric oxide magnetic nano composite
CN107662949A (en) * 2017-10-27 2018-02-06 成都理工大学 A kind of graphene oxide-loaded ferriferrous oxide nano composite and preparation method thereof
CN110841642A (en) * 2019-12-03 2020-02-28 哈尔滨工业大学 Preparation method of ultra-small ferroferric oxide compact coated three-dimensional reduced graphene oxide Fenton catalyst
CN111437882A (en) * 2020-04-10 2020-07-24 山东特龙谱新材料有限公司 Preparation method of magnetic composite membrane material doped with silicon-based heteropoly acid

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101941842A (en) * 2010-10-11 2011-01-12 东华大学 Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material
CN103030208A (en) * 2013-01-08 2013-04-10 哈尔滨工业大学 Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters
CN103341346A (en) * 2013-06-26 2013-10-09 江苏省环境科学研究院 Preparation method of manganese ferrite nanoparticle-graphene compound
CN105478078A (en) * 2015-11-25 2016-04-13 蚌埠学院 Preparation method and use of highly dispersed magnetic graphene nanometer adsorbent
CN106475100A (en) * 2016-08-30 2017-03-08 江苏金茂源生物化工有限责任公司 The preparation method and application of Graphene/ferroferric oxide magnetic nano composite
CN107662949A (en) * 2017-10-27 2018-02-06 成都理工大学 A kind of graphene oxide-loaded ferriferrous oxide nano composite and preparation method thereof
CN110841642A (en) * 2019-12-03 2020-02-28 哈尔滨工业大学 Preparation method of ultra-small ferroferric oxide compact coated three-dimensional reduced graphene oxide Fenton catalyst
CN111437882A (en) * 2020-04-10 2020-07-24 山东特龙谱新材料有限公司 Preparation method of magnetic composite membrane material doped with silicon-based heteropoly acid

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
HUAN-YAN XU ET AL.: "Nanoparticles of magnetite anchored onto few-layer graphene:A highly efficient Fenton-like nanocomposite catalyst", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 *
SHOU-QING LIU ET AL.: "Graphene oxide enhances the Fenton-like photocatalytic activity of nickel ferrite for degradation of dyes under visible light irradiation", 《CARBON》 *
付长璟: "《石墨烯的制备、结构及应用》", 30 June 2017 *
华南工学院等: "《陶瓷工艺学》", 31 July 1981, 中国建筑工业出版社 *
孙左一等, 水利电力出版社 *
李博: "亲水性石墨烯基Fenton催化剂的制备及效能评价", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
王瑞珏等: "四氧化三铁一石墨烯复合芬顿催化剂用于染料脱色的研究", 《西南民族大学学报（自然科学版）》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115254025A (en) * 2022-08-19 2022-11-01 常州大学 Preparation method of printing and dyeing sludge dehydrating agent and method for conditioning printing and dyeing sludge by using printing and dyeing sludge dehydrating agent
CN115254025B (en) * 2022-08-19 2024-04-05 常州大学 Preparation method of printing and dyeing sludge dehydrating agent and method for conditioning printing and dyeing sludge by using same

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