阅读说明：本技术 一种磁性纳米材料石墨烯-杆状四氧化三铁纳米复合体的制备方法 (Preparation method of magnetic nano material graphene-rod-shaped ferroferric oxide nano complex ) 是由 蔡开琳 欧阳君 古俊楠 曹英豪 郑昌敏 左华坤 刘胜林 邓胜和 毛富巍 薛一凡 于 2020-07-03 设计创作，主要内容包括：本发明公开了磁性材料生产技术领域的一种磁性纳米材料石墨烯-杆状四氧化三铁纳米复合体的制备方法,包括以下步骤：步骤一：S1：以石墨粉为原料采取Hummers法获得石墨烯,该种磁性纳米材料石墨烯-杆状四氧化三铁纳米复合体的制备方法,通过石墨烯修饰四氧化三铁颗粒,基于石墨烯的高机械强度、高表面积、导电性、体内稳定性、生物安全性等优异特性,应用于生物体内有更好的生物安全性以及不易被生物降解,有着石墨烯修饰后更强的稳定性、磁性等,也有着四氧化三铁杆状纳米颗粒带来的更强磁性,能够在生物医学、化工业、电磁学等多领域产生更广泛的应用,对于其在靶向治疗、磁热疗等生物医学领域以及电磁领域等的应用推动力更大。(The invention discloses a preparation method of a magnetic nano material graphene-rod-shaped ferroferric oxide nano complex, belonging to the technical field of magnetic material production, comprising the following steps: the method comprises the following steps: s1: according to the preparation method of the magnetic nano material graphene-rod-shaped ferroferric oxide nano complex, the ferroferric oxide particles are modified by graphene, and based on the excellent characteristics of high mechanical strength, high surface area, conductivity, in-vivo stability, biosafety and the like of the graphene, the magnetic nano material graphene-rod-shaped ferroferric oxide nano complex has better biosafety and is not easily biodegraded in organisms, has stronger stability, magnetism and the like after graphene modification and stronger magnetism brought by the ferroferric oxide rod-shaped nano particles, can be widely applied in the fields of biomedicine, chemical industry, electromagnetism and the like, and has larger application driving force in the biomedical fields of targeted therapy, magnetic thermotherapy and the like and the electromagnetic field and the like.)

1. A preparation method of a magnetic nano material graphene-rod-shaped ferroferric oxide nano complex is characterized by comprising the following steps: the method comprises the following steps:

the method comprises the following steps:

s1: graphite powder is used as a raw material, graphene is obtained by a Hummers method, a 500ml reaction bottle is assembled in an ice-water bath, 3g to 10g of graphite powder, 1g to 3g of sodium nitrate and 100ml to 120ml of concentrated sulfuric acid are uniformly mixed, stirred for 2min to 5min and then added with 12g to 18g of potassium perchlorate;

s2: adding 5-10 g of potassium permanganate in batches, keeping the temperature at 10-15 ℃, removing ice bath after fusion, continuously stirring a reaction bottle for 10-24 h by using an electromagnetic stirrer, gradually adding 150-200 ml of deionized water, gradually heating to 70-98 ℃, and stirring for 10-20 min;

s3: adding double-salt water to reduce residual oxidant, centrifugally separating graphite suspension at 8000-10000 rpm after the color of the solution is changed, washing with 2-4% HCL solution to make the PH value more than or equal to 6, and standing after the filter cake is dried;

step two:

s1: grinding the filter cake, weighing 150-250 mg, dispersing in 40-50 ml of fusion liquid to obtain suspension, and dispersing for 40-80 min by matching with ultrasonic to obtain stable colloidal suspension;

s2: transferring the mixture into a flask, adding a mixed solution, heating to 70-80 ℃, refluxing for 5-8 h, performing centrifugal separation, placing the mixture into a DEG solution, and performing ultrasonic treatment to obtain a graphene solution;

step three:

s1: the nano ferroferric oxide particles generated in situ on the graphene nano-sheets are prepared from Fe3+ and Fe2+, and the molar ratio is 1.5: 1 FeCl3 solution and FeSO 4.7H 2O;

s2: preparing ferroferric oxide particles by taking ferric chloride, ferrous sulfate and sodium hydroxide solution as raw materials, treating the three solutions under ultrasonic treatment, adding NaOH, and performing ultrasonic treatment for 15-20 min to generate black precipitates;

s3: the black precipitate is bathed for 15min to 30min at the temperature of 40 ℃ to 65 ℃ to separate out graphene-ferroferric oxide precipitate;

s4: and repeatedly washing the mixture for 3-5 times by using deionized water and ethanol to obtain the graphene-rod-shaped ferroferric oxide nano complex.

2. The preparation method of the magnetic nano-material graphene-rod-shaped ferroferric oxide nano-composite according to claim 1, characterized by comprising the following steps: the particle size of the graphite powder is less than 15-30 μm, the content is more than 80-95%, and the carbon content is 97-99.85%.

3. The preparation method of the magnetic nano-material graphene-rod-shaped ferroferric oxide nano-composite according to claim 1, characterized by comprising the following steps: the fusion liquid is deionized water.

4. The preparation method of the magnetic nano-material graphene-rod-shaped ferroferric oxide nano-composite according to claim 1, characterized by comprising the following steps: the compounding liquid is 400-600 mg of sodium borohydride and 30-50 mg of sodium dodecyl benzene sulfonate fusion.

5. The preparation method of the magnetic nano-material graphene-rod-shaped ferroferric oxide nano-composite according to claim 1, characterized by comprising the following steps: the mixing ratio of the deionized water to the ethanol is 4: 2-4: 2.5.

Technical Field

The invention discloses a preparation method of a magnetic nano material graphene-rod-shaped ferroferric oxide nano complex, and particularly relates to the technical field of magnetic material production.

Background

Biomedicine, which is a leading-edge interdisciplinary subject developed by combining theories and methods of medicine, life science and biology, is basically a task of researching and solving problems related to life science, particularly medicine, by using biological and engineering technical means, and includes many new materials, of which magnetic materials are an important component.

The magnetic material has been widely researched and applied in industry and medicine, and nowadays, the magnetic nano material has more outstanding advantages in biomedical application due to better physical and chemical properties and magnetic properties such as superparamagnetism, high magnetic energy product, difficult demagnetization and the like. The magnetic nano-materials comprise ferroferric oxide nano-particles with wide application and rare earth magnetic nano-particles such as neodymium iron boron, samarium cobalt, aluminum nickel cobalt and the like. In the preparation and application of magnetic nano materials, the biological modification of nano particles to improve the properties is very important, and the biological modification of nano particles comprises dextran, PEG, liposome, carboxymethyl chitosan and the like.

However, the modified magnetic material has weak stability and magnetism, and is difficult to be widely applied in the production in the fields of biomedicine, chemical industry, electromagnetism and the like, and the driving force is limited in the biomedicine fields such as targeted therapy, magnetic thermotherapy and the like, the electromagnetic field and the like, so that the application range and the effect are limited.

Disclosure of Invention

The invention aims to provide a preparation method of a magnetic nano material graphene-rod-shaped ferroferric oxide nano complex, which aims to solve the problems that the magnetic material modified in the background technology has weak stability and magnetism, is difficult to be widely applied in the production in the fields of biomedicine, chemical industry, electromagnetism and the like, has limited driving force in the biomedicine field such as targeted therapy, magnetic thermotherapy and the like, and has limited use range and effect in the electromagnetic field and the like.

In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a magnetic nano material graphene-rod-shaped ferroferric oxide nano complex comprises the following steps:

the method comprises the following steps:

s1: graphite powder is used as a raw material, graphene is obtained by a Hummers method, a 500ml reaction bottle is assembled in an ice-water bath, 3g to 10g of graphite powder, 1g to 3g of sodium nitrate and 100ml to 120ml of concentrated sulfuric acid are uniformly mixed, stirred for 2min to 5min and then added with 12g to 18g of potassium perchlorate;

s2: adding 5-10 g of potassium permanganate in batches, keeping the temperature at 10-15 ℃, removing ice bath after fusion, continuously stirring a reaction bottle for 10-24 h by using an electromagnetic stirrer, gradually adding 150-200 ml of deionized water, gradually heating to 70-98 ℃, and stirring for 10-20 min;

s3: adding double-salt water to reduce residual oxidant, centrifugally separating graphite suspension at 8000-10000 rpm after the color of the solution is changed, washing with 2-4% HCL solution to make the PH value more than or equal to 6, and standing after the filter cake is dried;

step two:

s1: grinding the filter cake, weighing 150-250 mg, dispersing in 40-50 ml of fusion liquid to obtain suspension, and dispersing for 40-80 min by matching with ultrasonic to obtain stable colloidal suspension;

s2: transferring the mixture into a flask, adding a mixed solution, heating to 70-80 ℃, refluxing for 5-8 h, performing centrifugal separation, placing the mixture into a DEG solution, and performing ultrasonic treatment to obtain a graphene solution;

step three:

s1: the nano ferroferric oxide particles generated in situ on the graphene nano-sheets are prepared from Fe3+ and Fe2+, and the molar ratio is 1.5: 1 FeCl3 solution and FeSO 4.7H 2O;

s2: preparing ferroferric oxide particles by taking ferric chloride, ferrous sulfate and sodium hydroxide solution as raw materials, treating the three solutions under ultrasonic treatment, adding NaOH, and performing ultrasonic treatment for 15-20 min to generate black precipitates;

s3: the black precipitate is bathed for 15min to 30min at the temperature of 40 ℃ to 65 ℃ to separate out graphene-ferroferric oxide precipitate;

s4: and repeatedly washing the mixture for 3-5 times by using deionized water and ethanol to obtain the graphene-rod-shaped ferroferric oxide nano complex.

Preferably, the content of the particles with the particle size of less than 15-30 μm of the graphite powder is more than 80-95 percent, and the carbon content is 97-99.85 percent.

Preferably, the fusion liquid is deionized water.

Preferably, the compounding solution is a fusion of 400 mg-600 mg of sodium borohydride and 30 mg-50 mg of sodium dodecyl benzene sulfonate.

Preferably, the mixing ratio of the deionized water to the ethanol is 4: 2-4: 2.5.

compared with the prior art, the invention has the beneficial effects that: according to the preparation method of the magnetic nano material graphene-rod-shaped ferroferric oxide nano complex, the ferroferric oxide particles are modified by the graphene, and based on the excellent characteristics of high mechanical strength, high surface area, conductivity, in-vivo stability, biological safety and the like of the graphene, the magnetic nano complex has better biological safety and is not easy to be biodegraded in organisms, stronger stability, magnetism and the like after the graphene is modified, stronger magnetism brought by the ferroferric oxide rod-shaped nano particles is also provided, the magnetic nano complex can be widely applied to various fields such as biomedicine, chemical industry, electromagnetism and the like, and a greater driving force can be generated for the application of the magnetic nano complex in the biomedical fields such as targeted therapy, magnetic thermotherapy and the like and in the electromagnetic field and the like.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a technical scheme that: a preparation method of a magnetic nano material graphene-rod-shaped ferroferric oxide nano complex comprises the following steps:

the method comprises the following steps:

s1: graphite powder is used as a raw material, graphene is obtained by a Hummers method, a 500ml reaction bottle is assembled in an ice-water bath, 3g to 10g of graphite powder, 1g to 3g of sodium nitrate and 100ml to 120ml of concentrated sulfuric acid are uniformly mixed, stirred for 2min to 5min and then added with 12g to 18g of potassium perchlorate;

s2: adding 5-10 g of potassium permanganate in batches, keeping the temperature at 10-15 ℃, removing ice bath after fusion, continuously stirring a reaction bottle for 10-24 h by using an electromagnetic stirrer, gradually adding 150-200 ml of deionized water, gradually heating to 70-98 ℃, and stirring for 10-20 min;

s3: adding double-salt water to reduce residual oxidant, centrifugally separating graphite suspension at 8000-10000 rpm after the color of the solution is changed, washing with 2-4% HCL solution to make the PH value more than or equal to 6, and standing after the filter cake is dried;

step two:

s1: grinding the filter cake, weighing 150-250 mg, dispersing in 40-50 ml of fusion liquid to obtain suspension, and dispersing for 40-80 min by matching with ultrasonic to obtain stable colloidal suspension;

s2: transferring the mixture into a flask, adding a mixed solution, heating to 70-80 ℃, refluxing for 5-8 h, performing centrifugal separation, placing the mixture into a DEG solution, and performing ultrasonic treatment to obtain a graphene solution;

step three:

s1: the nano ferroferric oxide particles generated in situ on the graphene nano-sheets are prepared from Fe3+ and Fe2+, and the molar ratio is 1.5: 1 FeCl3 solution and FeSO 4.7H 2O;

s2: preparing ferroferric oxide particles by taking ferric chloride, ferrous sulfate and sodium hydroxide solution as raw materials, treating the three solutions under ultrasonic treatment, adding NaOH, and performing ultrasonic treatment for 15-20 min to generate black precipitates;

s3: the black precipitate is bathed for 15min to 30min at the temperature of 40 ℃ to 65 ℃ to separate out graphene-ferroferric oxide precipitate;

s4: and repeatedly washing the mixture for 3-5 times by using deionized water and ethanol to obtain the graphene-rod-shaped ferroferric oxide nano complex.

Preferably, the content of the particles with the particle size of less than 15-30 μm of the graphite powder is more than 80-95 percent, and the carbon content is 97-99.85 percent.

Preferably, the fusion liquid is deionized water.

Preferably, the compounding solution is 400 mg-600 mg of sodium borohydride and 30 mg-50 mg of sodium dodecyl benzene sulfonate fusion.

Preferably, the mixing ratio of the deionized water to the ethanol is 4: 2-4: 25.