WO2018201715A1 - Graphene and ferroferric oxide@gold composite material and preparation method and application thereof - Google Patents

Graphene and ferroferric oxide@gold composite material and preparation method and application thereof Download PDF

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WO2018201715A1
WO2018201715A1 PCT/CN2017/114624 CN2017114624W WO2018201715A1 WO 2018201715 A1 WO2018201715 A1 WO 2018201715A1 CN 2017114624 W CN2017114624 W CN 2017114624W WO 2018201715 A1 WO2018201715 A1 WO 2018201715A1
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graphene
oxide
ferroferric oxide
gold composite
gold
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PCT/CN2017/114624
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French (fr)
Chinese (zh)
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黄国家
李茂东
杨波
辛明亮
尹宗杰
张双红
李仕平
翟伟
***
黎佩珊
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广州特种承压设备检测研究院
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Priority to US16/313,725 priority Critical patent/US20190168298A1/en
Publication of WO2018201715A1 publication Critical patent/WO2018201715A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/40—Carbon, graphite

Definitions

  • the invention relates to the field of materials, in particular to a graphene and a ferroferric oxide@gold composite material and a preparation method and application thereof.
  • graphene has a high dielectric constant, which is polarized by an external magnetic field in an electromagnetic field, and an internal electric dipole of a graphene material. Relaxation occurs as the electric field moves, consuming some of the electrical energy to cause the dielectric itself to heat up, ie, dielectric loss.
  • a single graphene sheet is easily penetrated by electromagnetic waves to lose electromagnetic wave absorption capability, and a single high dielectric loss also causes difficulty in impedance matching.
  • ferroferric oxide has ferromagnetism, it is a good microwave absorber and nuclear magnetic contrast agent.
  • CN106501235A discloses a method for detecting Vibrio parahaemolyticus based on enhanced Raman effect of graphene oxide/ferric oxide/colloidal gold nanoparticles, wherein the connection system of the oxide oxide/ferric oxide/colloidal gold nanoparticles is unstable. . Therefore, how to prepare a stable multi-functional composite material is of great significance.
  • a method for preparing graphene and ferroferric oxide@gold composite material comprises the following steps:
  • the azide thiol-modified ferroferric oxide@gold composite comprises the following construction steps:
  • the ferroferric oxide@gold composite and the azide thiol are placed in a first solvent, and the reaction is stirred at 40 to 45 ° C under a protective gas atmosphere, and repeatedly washed with a second solvent to obtain the Azidothiol-modified triiron tetroxide@gold composite;
  • the alkynylated graphene oxide comprises the following construction steps:
  • the graphene oxide is placed in an activator for activation reaction, and then propargyl alcohol is added to continue the reaction for 20-28 h to obtain the alkynylated graphene oxide;
  • the mass ratio of the azidosulfide-modified ferroferric oxide@gold composite to the alkynylated graphene oxide is 30 to 50: 30 to 50.
  • the third solvent is dimethylformamide or tetrahydrofuran
  • the catalyst is N, N, N', N", N"-pentamethyldiene.
  • Ethyltriamine and cuprous bromide is N, N, N', N", N"-pentamethyldiene.
  • the number of carbon atoms in the azide thiol is N, 6 ⁇ N ⁇ 15; the triiron tetroxide @ gold complex and azide
  • the mass ratio of mercaptan is 100:0.4 to 2.
  • the activator is thionyl chloride, and the activation reaction time of the graphene oxide in the thionyl chloride is 20 to 28 h.
  • the first solvent is toluene; the second solvent is a non-polar solvent, the ferroferric oxide@gold complex and the azide thiol
  • the reaction time is 45 to 55 h.
  • the nano-ferric oxide comprises the following steps: dissolving 1.8-2.2 g of FeCl 3 ⁇ 6H 2 O in 100 ⁇ 5 mL of distilled water under a nitrogen atmosphere. Under the condition of neutralization and stirring, 0.8-1.2g of FeCl 2 ⁇ 4H 2 O is added, and then the ammonia or sodium hydroxide solution is added dropwise until the pH of the reaction liquid rises to 8.8-9.5, and then heated to 80 ° C to 90 ° C for the reaction 20 ⁇ 30min, the magnetic separation, the nanometer ferroferric oxide;
  • the reducing agent has a mass concentration of 1 to 3 mg/mL and a volume of 100 ⁇ 5 mL; the aqueous solution of the chloroauric acid has a mass concentration of 8 to 12 mg/mL, and the volume of the addition is 8 to 12 mL.
  • the preparation process of the graphene oxide comprises the following steps:
  • the reaction system is heated to 28 to 32 ° C for 55 to 65 minutes, and then 15 to 25 mL of deionized water is added to the reaction system, and the temperature is raised to 90 to 99 ° C, and the reaction is continued for 13 to 17 minutes, and then 65 is added.
  • deionized water add 2.0 ⁇ 3.0mL hydrogen peroxide, remove excess potassium permanganate, the solution is bright yellow, let stand for one day, remove the supernatant, wash the lower yellow solid with deionized water, rinse repeatedly There is no acid and sulfate ion in the supernatant, and freeze-drying, that is, the graphene oxide is obtained.
  • a graphene and a ferroferric oxide@gold composite material prepared by the above preparation method of graphene and ferroferric oxide@gold composite material.
  • the preparation method of the graphene and the ferroferric oxide@gold composite material of the invention firstly prepares the triiron tetroxide@gold composite by a one-pot method, and the content of the coated gold is high, and then the azide thiol-modified four is further constructed.
  • the triironium-gold composite is formed to form a gold-sulfur bond on the surface of the nano gold, and the graphene oxide is activated by an activator to react the carboxyl group on the surface of the graphene oxide with the propargyl alcohol to form an alkynyl graphene oxide, and then two Under the nitrogen atmosphere, the alkynyl group and the azide group are subjected to a click reaction by a catalyst, and the reaction speed is fast and the efficiency is high, thereby obtaining a graphene and a ferroferric oxide@gold composite material which are connected by an organic covalent bond.
  • the preparation method of the graphene and the ferroferric oxide@gold composite material of the invention has mild reaction conditions, and the preparation method is simple and reliable.
  • the graphene of the invention and the ferroferric oxide@gold composite material are connected by a covalent bond to stabilize the system of the graphene and the ferroferric oxide@gold composite material, and at the same time, the graphene and the ferroferric oxide@gold composite material are simultaneously made.
  • magnetic properties good microwave absorption, good plasmon resonance absorption and attenuation of X-ray, it can be applied to both nuclear magnetic imaging, microwave thermoacoustic imaging, photoacoustic imaging and X-ray imaging.
  • Example 1 is a transmission electron micrograph of a ferroferric oxide@gold composite obtained in the preparation of Example 1.
  • Example 2 is a concentration-signal response diagram of the graphene and the ferroferric oxide@gold composite material prepared in Example 1 in a nuclear magnetic imaging application;
  • Example 3 is a concentration-signal response diagram of the graphene and the ferroferric oxide@gold composite material prepared in Example 1 in photoacoustic imaging applications;
  • Example 4 is a concentration-signal response diagram of the graphene and the ferroferric oxide@gold composite material prepared in Example 1 in a microwave thermoacoustic imaging application;
  • Example 5 is a concentration-signal response diagram of graphene and triiron tetroxide @gold composite material prepared in Example 1 in X-ray imaging applications.
  • the embodiment provides a method for preparing graphene and a ferroferric oxide@gold composite material, comprising the following steps:
  • the azide thiol-modified ferroferric oxide@gold composite comprises the following construction steps:
  • the nano-colloidal solution of nano-ferric oxide obtained in step A was magnetically separated to obtain solid particles, which were washed three times with 2 mg/mL sodium citrate aqueous solution, dissolved in 100 mL of the same concentration of sodium citrate aqueous solution, and placed in an ultrasonic machine. Medium sonication for 7 h; the sonicated mixture was placed in a three-necked flask, and the mixture was heated to 70 ° C under stirring, and 10 mL of 10 mg/mL aqueous solution of HAuCl 4 was slowly added dropwise under stirring to continue the reaction for 1 h.
  • a rice-ferric tetroxide @(coated) gold composite is prepared by a one-pot method, so that the gold content is high and the construction efficiency is high.
  • the transmission electron microscope of the obtained ferroferric oxide@gold composite obtained in this step is shown in Fig. 1.
  • the nanometer ferroferric oxide@gold composite has a small average particle diameter, a large particle size, and a good overall dispersibility.
  • step B Take 40 mg of the ferroferric oxide @gold complex obtained in step B and 0.2 mg of azide thiol (N 3 -(CH 2 ) n -SH, 6 ⁇ n ⁇ 15), and place it in toluene at 40 ⁇ .
  • the reaction was stirred at 45 ° C under nitrogen for 48 h with stirring; then washed repeatedly with n-hexane or toluene to remove excess unmodified upper segments.
  • the gold-sulfur bond is formed on the surface of the nano gold by constructing an azide-thiol-modified ferroferric oxide@gold composite.
  • Alkynylated graphene oxide includes the following construction steps:
  • step (1) Adding 40 mg of the azide thiol-modified Fe3O4 gold complex and 40 mg of alkynylated graphene oxide in step (1) to 20 mL of dimethylformamide or tetrahydrofuran, and adding 0.01 mL N, N, N', N", N"-pentamethyldiethylenetriamine and 6 mg of cuprous bromide were used as catalysts, and the reaction was stirred for 48 hours under a nitrogen atmosphere.
  • the sulfhydryl group at one end of the azide thiol forms a gold-sulfur bond with the surface of the ferroferric oxide/gold complex, and the azide group at the other end forms a click reaction with the alkyne group in the alkynyl graphene oxide.
  • the product is dissolved in dimethylformamide or tetrahydrofuran, and the product is collected by filtration to obtain.
  • the graphene prepared in Example 1 and the triiron tetroxide @gold composite material were prepared to have a concentration gradient of 0 mmoL/L, 0.1 mmoL/L, 0.2 mmoL/L, 0.4 mmoL/L, and 0.8 mmoL.
  • /L and 1mmoL/L G-Fe 3 O 4 @Au nanoparticle solution used in nuclear magnetic imaging, photoacoustic imaging and microwave thermoacoustic imaging, the concentration-signal response curves are shown in Figure 2, Figure 3 and Figure 4, respectively.
  • the graphene prepared in Example 1 and the ferroferric oxide @ ⁇ composite material were prepared to have a concentration gradient of 1 mg/mL, 2 mg/mL, 4 mg/mL and 8 mg/mL, respectively.
  • the imaging marks No. 4, 3, 2 and 1 are shown in Fig. 5.
  • the color depth of the X-ray image is deepened as the mass concentration of G-Fe 3 O 4 @Au increases.

Abstract

A preparation method for use with a graphene and ferroferric oxide@gold composite material, and a product and application thereof. A preparation process for the graphene and ferroferric oxide@gold composite material is as follows: first, constructing an azide thiol-modified ferroferric oxide@gold complex; activating graphene oxide by means of dichlorosulfoxide and then reacting with propargyl alcohol to form alkynyl graphene oxide; next catalyzing the two under a nitrogen atmosphere such that a click reaction occurs between an alkynyl group and an azide group, thereby obtaining the composite material. Reaction conditions of the preparation method for use with the graphene and ferroferric oxide@gold composite material are mild, and the preparation method is simple and reliable. The graphene and ferroferric oxide@gold composite material is connected by means of a covalent bond such that the system is stable, and has the features of good magnetic and microwave absorption performance, good plasma resonance absorption and attenuation of X-rays. The present invention may be applied in nuclear magnetic imaging, microwave thermoacoustic imaging, photoacoustic imaging and X-ray imaging.

Description

石墨烯与四氧化三铁@金复合材料及其制备方法和应用Graphene and ferroferric oxide@金 composite material and preparation method and application thereof 技术领域Technical field
本发明涉及材料领域，特别是涉及一种石墨烯与四氧化三铁@金复合材料及其制备方法和应用。The invention relates to the field of materials, in particular to a graphene and a ferroferric oxide@gold composite material and a preparation method and application thereof.
背景技术Background technique
在纳米技术快速发展的今天，单一成份材料的功能具有较大局限性，例如，石墨烯具有很高的介电常数，在电磁场中会被外磁场极化，而石墨烯材料内部电偶极子随电场运动而发生弛豫，消耗部分电能而使电介质本身发热，即产生介电损耗。单一的石墨烯片层易被电磁波穿透而失去电磁波吸收能力，同时，单一的高介电损耗也会导致阻抗匹配的困难。而四氧化三铁具有铁磁性，是一种良好的微波吸收剂和核磁造影剂。通过将石墨烯与四氧化三铁进行复合，可以使电磁波透入复合材料后受到量子点阵间势垒作用以及空间位阻效应的阻碍延缓电磁波的直接透过，从而起到降低电磁波频率效果。纳米金表面等离子体共振效应使其具有良好光学吸收性质和光热转换效应。CN106501235A公开了基于氧化石墨烯/四氧化三铁/胶体金纳米粒子增强拉曼效应的副溶血性弧菌检测方法，其中的氧化石烯/四氧化三铁/胶体金纳米粒子的连接体系不稳定。因此，如何制备出体系稳定的多功能复合材料具有重要的意义。In the rapid development of nanotechnology, the function of single component materials has great limitations. For example, graphene has a high dielectric constant, which is polarized by an external magnetic field in an electromagnetic field, and an internal electric dipole of a graphene material. Relaxation occurs as the electric field moves, consuming some of the electrical energy to cause the dielectric itself to heat up, ie, dielectric loss. A single graphene sheet is easily penetrated by electromagnetic waves to lose electromagnetic wave absorption capability, and a single high dielectric loss also causes difficulty in impedance matching. While ferroferric oxide has ferromagnetism, it is a good microwave absorber and nuclear magnetic contrast agent. By combining graphene and ferroferric oxide, electromagnetic waves can be transmitted into the composite material, which is hindered by the interaction between the quantum dot matrix and the steric hindrance effect, thereby delaying the direct transmission of electromagnetic waves, thereby reducing the electromagnetic wave frequency effect. The nano-gold surface plasmon resonance effect makes it have good optical absorption properties and photothermal conversion effects. CN106501235A discloses a method for detecting Vibrio parahaemolyticus based on enhanced Raman effect of graphene oxide/ferric oxide/colloidal gold nanoparticles, wherein the connection system of the oxide oxide/ferric oxide/colloidal gold nanoparticles is unstable. . Therefore, how to prepare a stable multi-functional composite material is of great significance.
发明内容Summary of the invention
基于此，有必要提供一种能够体系稳定的石墨烯与四氧化三铁@(包覆)金复合材料及其制备方法和应用。Based on this, it is necessary to provide a system-stabilized graphene and triiron tetroxide @(coated) gold composite material and a preparation method and application thereof.
一种石墨烯与四氧化三铁@金复合材料的制备方法，包括如下步骤：A method for preparing graphene and ferroferric oxide@gold composite material comprises the following steps:
(1)构建叠氮化硫醇修饰的四氧化三铁@金复合体和炔基化的氧化石墨烯：(1) Construction of azidothiol-modified triiron tetroxide @gold composite and alkynylated graphene oxide:
其中，所述叠氮化硫醇修饰的四氧化三铁@金复合体包括如下构建步骤：Wherein, the azide thiol-modified ferroferric oxide@gold composite comprises the following construction steps:
将纳米四氧化三铁分散于还原剂溶液中，超声处理，加热至65℃～75℃，在搅拌条件下滴加氯金酸水溶液，反应后停止加热，再搅拌熟化反应，获得具有 核壳结构的四氧化三铁@金复合体；Dispersing the nanometer iron trioxide in the reducing agent solution, sonicating, heating to 65 ° C ~ 75 ° C, adding chloroauric acid aqueous solution under stirring, stopping the heating after the reaction, and stirring the ripening reaction to obtain Core-shell structure of ferroferric oxide @金复合体;
将所述四氧化三铁@金复合体和叠氮化硫醇置于第一溶剂中，在40～45℃条件下和在保护气氛围中搅拌反应，用第二溶剂反复冲洗，获得所述叠氮化硫醇修饰的四氧化三铁@金复合体；The ferroferric oxide@gold composite and the azide thiol are placed in a first solvent, and the reaction is stirred at 40 to 45 ° C under a protective gas atmosphere, and repeatedly washed with a second solvent to obtain the Azidothiol-modified triiron tetroxide@gold composite;
所述炔基化的氧化石墨烯包括如下构建步骤：The alkynylated graphene oxide comprises the following construction steps:
在65～75℃条件下，将氧化石墨烯置于活化剂中进行活化反应，再加入炔丙醇继续反应20～28h，得到所述炔基化的氧化石墨烯；At 65-75 ° C, the graphene oxide is placed in an activator for activation reaction, and then propargyl alcohol is added to continue the reaction for 20-28 h to obtain the alkynylated graphene oxide;
(2)构建石墨烯与四氧化三铁@金复合材料：(2) Construction of graphene and ferroferric oxide @金 composite materials:
将步骤(1)构建的所述叠氮化硫醇修饰的四氧化三铁@金复合体和所述炔基化的氧化石墨烯分散在第三溶剂中，加入催化剂，在保护气氛围中，搅拌反应，收集产物，即得。Dispersing the azide thiol-modified ferritic oxide-gold composite and the alkynylated graphene oxide in the third solvent in the step (1), adding a catalyst, in a protective gas atmosphere, The reaction was stirred and the product was collected to give.
在其中一个实施例中，在步骤(2)中，所述叠氮化硫醇修饰的四氧化三铁@金复合体和所述炔基化的氧化石墨烯的质量浓度比为30～50:30～50。In one embodiment, in the step (2), the mass ratio of the azidosulfide-modified ferroferric oxide@gold composite to the alkynylated graphene oxide is 30 to 50: 30 to 50.
在其中一个实施例中，在步骤(2)中，所述第三溶剂为二甲基甲酰胺或四氢呋喃，所述催化剂为N,N,N',N″,N″-五甲基二亚乙基三胺和溴化亚铜。In one embodiment, in the step (2), the third solvent is dimethylformamide or tetrahydrofuran, and the catalyst is N, N, N', N", N"-pentamethyldiene. Ethyltriamine and cuprous bromide.
在其中一个实施例中，在步骤(1)中，所述叠氮化硫醇中碳原子的个数为N，6＜N＜15；所述四氧化三铁@金复合体和叠氮化硫醇的质量比为100:0.4～2。In one embodiment, in the step (1), the number of carbon atoms in the azide thiol is N, 6 < N < 15; the triiron tetroxide @ gold complex and azide The mass ratio of mercaptan is 100:0.4 to 2.
在其中一个实施例中，在步骤(1)中，所述活化剂为二氯亚砜，所述氧化石墨烯在所述二氯亚砜中的活化反应时间为20～28h。In one embodiment, in the step (1), the activator is thionyl chloride, and the activation reaction time of the graphene oxide in the thionyl chloride is 20 to 28 h.
在其中一个实施例中，在步骤(1)中，所述第一溶剂为甲苯；所述第二溶剂为非极性溶剂，所述四氧化三铁@金复合体和叠氮化硫醇的反应时间为45～55h。In one embodiment, in the step (1), the first solvent is toluene; the second solvent is a non-polar solvent, the ferroferric oxide@gold complex and the azide thiol The reaction time is 45 to 55 h.
在其中一个实施例中，在步骤(1)中，所述纳米四氧化三铁包括如下制备步骤：将1.8～2.2g的FeCl3·6H2O溶解在100±5mL的蒸馏水中，在氮气氛围中和搅拌条件下加入0.8～1.2g的FeCl2·4H2O，再滴加氨水或氢氧化钠溶液至反应液的pH升至8.8～9.5，再加热至80℃～90℃条件下反应20～30min，经磁性分离，即得所述纳米四氧化三铁；In one embodiment, in the step (1), the nano-ferric oxide comprises the following steps: dissolving 1.8-2.2 g of FeCl 3 ·6H 2 O in 100±5 mL of distilled water under a nitrogen atmosphere. Under the condition of neutralization and stirring, 0.8-1.2g of FeCl 2 ·4H 2 O is added, and then the ammonia or sodium hydroxide solution is added dropwise until the pH of the reaction liquid rises to 8.8-9.5, and then heated to 80 ° C to 90 ° C for the reaction 20 ~30min, the magnetic separation, the nanometer ferroferric oxide;
在所述叠氮化硫醇修饰的四氧化三铁@金复合体的构建步骤中，所述还原剂 为柠檬酸钠，所述柠檬酸钠的质量浓度为1～3mg/mL，体积为100±5mL；所述氯金酸水溶液的质量浓度为8～12mg/mL，加入体积为8～12mL。In the step of constructing the azide thiol-modified triiron tetroxide@gold complex, the reducing agent The sodium citrate has a mass concentration of 1 to 3 mg/mL and a volume of 100 ± 5 mL; the aqueous solution of the chloroauric acid has a mass concentration of 8 to 12 mg/mL, and the volume of the addition is 8 to 12 mL.
在其中一个实施例中，在步骤(1)中，所述氧化石墨烯的制备过程包括如下步骤：In one embodiment, in the step (1), the preparation process of the graphene oxide comprises the following steps:
在冰浴条件下，向0.4～0.6g天然石墨、0.5～0.6g硝酸钠的混合体系中加入13～17mL浓硫酸，再加入1.3～1.7g高锰酸钾，并保持反应体系的温度不高于5℃；Under ice bath conditions, add 13 to 17 mL of concentrated sulfuric acid to a mixed system of 0.4 to 0.6 g of natural graphite and 0.5 to 0.6 g of sodium nitrate, and then add 1.3 to 1.7 g of potassium permanganate, and keep the temperature of the reaction system low. At 5 ° C;
加料完毕后，将上述反应体系加热至28～32℃条件下反应55～65min，再向该反应体系加入15～25mL去离子水，升温至90～99℃，继续反应13～17min，再加入65～75mL去离子水，再滴加2.0～3.0mL双氧水，除去过量的高锰酸钾，此时溶液为亮黄色，静置一天，去上清液，用去离子水洗涤下层黄色固体，反复冲洗至上清液中无酸性和硫酸根离子，冷冻干燥，即得所述氧化石墨烯。After the addition is completed, the reaction system is heated to 28 to 32 ° C for 55 to 65 minutes, and then 15 to 25 mL of deionized water is added to the reaction system, and the temperature is raised to 90 to 99 ° C, and the reaction is continued for 13 to 17 minutes, and then 65 is added. ~75mL deionized water, add 2.0 ~ 3.0mL hydrogen peroxide, remove excess potassium permanganate, the solution is bright yellow, let stand for one day, remove the supernatant, wash the lower yellow solid with deionized water, rinse repeatedly There is no acid and sulfate ion in the supernatant, and freeze-drying, that is, the graphene oxide is obtained.
一种由上述石墨烯与四氧化三铁@金复合材料的制备方法制备获得的石墨烯与四氧化三铁@金复合材料。A graphene and a ferroferric oxide@gold composite material prepared by the above preparation method of graphene and ferroferric oxide@gold composite material.
上述石墨烯与四氧化三铁@金复合材料在核磁成像、微波热声成像、光声成像、X光成像中的应用。The above-mentioned application of graphene and ferroferric oxide@gold composite materials in nuclear magnetic imaging, microwave thermoacoustic imaging, photoacoustic imaging, and X-ray imaging.
本发明具有如下有益效果：The invention has the following beneficial effects:
本发明的石墨烯与四氧化三铁@金复合材料的制备方法，首先通过一锅法制备四氧化三铁@金复合体，包覆金的含量高，再构建叠氮化硫醇修饰的四氧化三铁@金复合体以使纳米金表面形成金硫键，通过活化剂活化氧化石墨烯使氧化石墨烯表面的羧基与炔丙醇发生反应构建形成炔基化的氧化石墨烯，再将两者在氮气氛围条件下经催化剂作用使炔基与叠氮基发生点击反应，反应速度快且效率高，进而获得通过有机共价键连接的石墨烯与四氧化三铁@金复合材料。本发明的石墨烯与四氧化三铁@金复合材料的制备方法的反应条件温和，制备方法简单可靠。本发明的石墨烯与四氧化三铁@金复合材料通过共价键连接，使该石墨烯与四氧化三铁@金复合材料的体系稳定，同时使石墨烯与四氧化三铁@金复合材料具磁性、微波吸收性能好、等离子体共振吸收好以及对X光衰减的特性，能够同时应用于核磁成像、微波热声成像、光声成像及X光成像。 The preparation method of the graphene and the ferroferric oxide@gold composite material of the invention firstly prepares the triiron tetroxide@gold composite by a one-pot method, and the content of the coated gold is high, and then the azide thiol-modified four is further constructed. The triironium-gold composite is formed to form a gold-sulfur bond on the surface of the nano gold, and the graphene oxide is activated by an activator to react the carboxyl group on the surface of the graphene oxide with the propargyl alcohol to form an alkynyl graphene oxide, and then two Under the nitrogen atmosphere, the alkynyl group and the azide group are subjected to a click reaction by a catalyst, and the reaction speed is fast and the efficiency is high, thereby obtaining a graphene and a ferroferric oxide@gold composite material which are connected by an organic covalent bond. The preparation method of the graphene and the ferroferric oxide@gold composite material of the invention has mild reaction conditions, and the preparation method is simple and reliable. The graphene of the invention and the ferroferric oxide@gold composite material are connected by a covalent bond to stabilize the system of the graphene and the ferroferric oxide@gold composite material, and at the same time, the graphene and the ferroferric oxide@gold composite material are simultaneously made. With magnetic properties, good microwave absorption, good plasmon resonance absorption and attenuation of X-ray, it can be applied to both nuclear magnetic imaging, microwave thermoacoustic imaging, photoacoustic imaging and X-ray imaging.
附图说明DRAWINGS
图1为实施例1制备获得的四氧化三铁@金复合体的透射电镜图；1 is a transmission electron micrograph of a ferroferric oxide@gold composite obtained in the preparation of Example 1.
图2为实施例1制备获得的石墨烯与四氧化三铁@金复合材料在核磁成像应用中的浓度-信号响应图；2 is a concentration-signal response diagram of the graphene and the ferroferric oxide@gold composite material prepared in Example 1 in a nuclear magnetic imaging application;
图3为实施例1制备获得的石墨烯与四氧化三铁@金复合材料在光声成像应用中的浓度-信号响应图；3 is a concentration-signal response diagram of the graphene and the ferroferric oxide@gold composite material prepared in Example 1 in photoacoustic imaging applications;
图4为实施例1制备获得的石墨烯与四氧化三铁@金复合材料在微波热声成像应用中的浓度-信号响应图；4 is a concentration-signal response diagram of the graphene and the ferroferric oxide@gold composite material prepared in Example 1 in a microwave thermoacoustic imaging application;
图5为实施例1制备获得的石墨烯与四氧化三铁@金复合材料在X光成像应用中的浓度-信号响应图。5 is a concentration-signal response diagram of graphene and triiron tetroxide @gold composite material prepared in Example 1 in X-ray imaging applications.
具体实施方式detailed description
下面结合具体的实施例对本发明的石墨烯与四氧化三铁@金复合材料(简称G-Fe3O4@Au)及其制备方法和应用做详细的说明。The graphene and the ferroferric oxide@gold composite material (G-Fe 3 O 4 @Au) and the preparation method and application thereof will be described in detail below with reference to specific examples.
实施例1Example 1
本实施例提供一种石墨烯与四氧化三铁@金复合材料的制备方法，包括如下步骤：The embodiment provides a method for preparing graphene and a ferroferric oxide@gold composite material, comprising the following steps:
(1)构建叠氮化硫醇修饰的四氧化三铁@金复合体和炔基化的氧化石墨烯：(1) Construction of azidothiol-modified triiron tetroxide @gold composite and alkynylated graphene oxide:
其中，叠氮化硫醇修饰的四氧化三铁@金复合体包括如下构建步骤：Wherein, the azide thiol-modified ferroferric oxide@gold composite comprises the following construction steps:
A、采用共沉淀法制备纳米四氧化三铁的胶体溶液A. Preparation of colloidal solution of nanometer ferric oxide by coprecipitation method
将2.703g的FeCl3·6H2O置于四口反应烧瓶体系中，加入100mL三蒸水使其溶解，通氮气保护，在搅拌条件加入0.998g的FeCl2·4H2O，将氨水从进样口逐滴滴加至反应体系中使溶液的pH升至9.2，停止加氨水，继续反应15min，再将反应体系加热至85℃,继续25min，得纳米四氧化三铁的胶体溶液。2.703g of FeCl 3 ·6H 2 O was placed in a four-neck reaction flask system, dissolved in 100 mL of three distilled water, protected by nitrogen, and 0.998 g of FeCl 2 ·4H 2 O was added under stirring to remove ammonia water. The sample was added dropwise to the reaction system to raise the pH of the solution to 9.2, the ammonia solution was stopped, the reaction was continued for 15 min, and the reaction system was heated to 85 ° C for 25 min to obtain a colloidal solution of nanometer ferroferric oxide.
B、采用还原法制备纳米四氧化三铁@(包覆)金复合体B. Preparation of nanometer ferroferric oxide @(coated) gold composite by reduction method
将步骤A获得的纳米四氧化三铁的胶体溶液20mL进行磁分离获得固体颗粒，用2mg/mL的柠檬酸钠水溶液洗涤3次后溶于100mL相同浓度的柠檬酸钠 水溶液中，置于超声机中超声7h；将超声处理后的混合液置于三口烧瓶中，在搅拌条件下，将该混合液加热至70℃，在搅拌条件下缓慢滴加10mL 10mg/mL的HAuCl4水溶液，继续反应1h后，停止加热，再搅拌熟化40min后停止反应，即得纳米四氧化三铁@(包覆)金复合体。该步骤采用一锅法制备米四氧化三铁@(包覆)金复合体，使金的包含量高，构建效率高。The nano-colloidal solution of nano-ferric oxide obtained in step A was magnetically separated to obtain solid particles, which were washed three times with 2 mg/mL sodium citrate aqueous solution, dissolved in 100 mL of the same concentration of sodium citrate aqueous solution, and placed in an ultrasonic machine. Medium sonication for 7 h; the sonicated mixture was placed in a three-necked flask, and the mixture was heated to 70 ° C under stirring, and 10 mL of 10 mg/mL aqueous solution of HAuCl 4 was slowly added dropwise under stirring to continue the reaction for 1 h. After that, the heating was stopped, and the reaction was stopped after stirring for 40 minutes to obtain a nano-ferric oxide @(coated) gold composite. In this step, a rice-ferric tetroxide @(coated) gold composite is prepared by a one-pot method, so that the gold content is high and the construction efficiency is high.
该步骤制备获得的四氧化三铁@金复合体的透射电镜见图1。由图1可知，纳米四氧化三铁@金复合体的平均粒径小，粒径集中，且整体的分散性好。The transmission electron microscope of the obtained ferroferric oxide@gold composite obtained in this step is shown in Fig. 1. As can be seen from Fig. 1, the nanometer ferroferric oxide@gold composite has a small average particle diameter, a large particle size, and a good overall dispersibility.
C、采用叠氮化硫醇修饰四氧化三铁@金复合体C. Modification of ferroferric oxide @金复合体 using azide thiol
取步骤B获得的四氧化三铁@金复合体40mg和和叠氮化硫醇(N3-(CH2)n-SH，6<n<15)0.2mg，置于甲苯中，在40～45℃和氮气环境中，在搅拌条件下，搅拌反应48h；然后用正己烷或甲苯反复冲洗，去除多余的未修饰上链段。通过构建叠氮化硫醇修饰的四氧化三铁@金复合体以使纳米金表面形成金硫键。Take 40 mg of the ferroferric oxide @gold complex obtained in step B and 0.2 mg of azide thiol (N 3 -(CH 2 ) n -SH, 6 < n < 15), and place it in toluene at 40 ～. The reaction was stirred at 45 ° C under nitrogen for 48 h with stirring; then washed repeatedly with n-hexane or toluene to remove excess unmodified upper segments. The gold-sulfur bond is formed on the surface of the nano gold by constructing an azide-thiol-modified ferroferric oxide@gold composite.
炔基化的氧化石墨烯包括如下构建步骤：Alkynylated graphene oxide includes the following construction steps:
取0.5g天然石墨、0.55g硝酸钠装入三口烧瓶中，将该三口烧瓶置于冰浴中，向瓶中慢慢加入15mL浓硫酸，并不停搅拌，之后缓慢加入1.5g高锰酸钾以保证烧瓶内温度不高于5℃，加完反应原料之后在30℃条件下，反应1h。再向三口烧瓶中加入去离子水20mL，将该反应体系升温至95℃，保持15min。再加入70mL去离子水，并逐滴加入2.5mL双氧水以除去多余高锰酸钾，此时溶液变成亮黄色。将混合物静置一天，倾倒出上层的酸液。将下层的黄色固体用去离子洗涤离心，弃去上层清夜，反复多次洗涤，直至上清液中无酸性和硫酸根离子，洗涤后的样品用冷冻干燥机低温冷冻干燥，即得氧化石墨烯。0.5 g of natural graphite and 0.55 g of sodium nitrate were placed in a three-necked flask. The three-necked flask was placed in an ice bath, and 15 mL of concentrated sulfuric acid was slowly added to the bottle, stirring was continued, and then 1.5 g of potassium permanganate was slowly added. In order to ensure that the temperature in the flask is not higher than 5 ° C, after adding the reaction raw materials, the reaction is carried out at 30 ° C for 1 h. Further, 20 mL of deionized water was added to the three-necked flask, and the reaction system was heated to 95 ° C for 15 min. An additional 70 mL of deionized water was added and 2.5 mL of hydrogen peroxide was added dropwise to remove excess potassium permanganate, at which point the solution turned bright yellow. The mixture was allowed to stand for one day and the upper layer of acid was poured out. The lower yellow solid was centrifuged by deionization, the supernatant was discarded, and the washing was repeated several times until there was no acid or sulfate ion in the supernatant. The washed sample was freeze-dried by a freeze dryer to obtain graphene oxide. .
在65～75℃条件下，将上步获得的氧化石墨烯1g置于0.1mL的二氯亚砜中活化24h，再加入炔丙醇继续反应24小时，得到炔基化的氧化石墨烯。该步骤通过二氯亚砜活化氧化石墨烯使氧化石墨烯表面的羧基与炔丙醇发生反应构建形成炔基化的氧化石墨烯。1 g of graphene oxide obtained in the previous step was placed in 0.1 mL of thionyl chloride for 24 h at 65 to 75 ° C, and then propargyl alcohol was added to continue the reaction for 24 hours to obtain alkynylated graphene oxide. This step is carried out by reacting graphene oxide with thionyl chloride to react a carboxyl group on the surface of the graphene oxide with propargyl alcohol to form an alkynylated graphene oxide.
(2)构建石墨烯与四氧化三铁@金复合材料：(2) Construction of graphene and ferroferric oxide @金 composite materials:
将步骤(1)构建的叠氮化硫醇修饰的四氧化三铁@金复合体40mg和炔基化的氧化石墨烯40mg加入到20mL二甲基甲酰胺或四氢呋喃中，加入0.01mL的 N,N,N',N″,N″-五甲基二亚乙基三胺和6mg溴化亚铜作为催化剂，在氮气氛围中，搅拌反应48h。在该步骤中，叠氮化硫醇一端的巯基与四氧化三铁@金复合体的表面形成金硫键，另一端的叠氮基与炔基化氧化石墨烯中的炔基发点击反应形成共价连接，反应结束后，将产物溶于二甲基甲酰胺或四氢呋喃中，然后过滤收集产物，即得。Adding 40 mg of the azide thiol-modified Fe3O4 gold complex and 40 mg of alkynylated graphene oxide in step (1) to 20 mL of dimethylformamide or tetrahydrofuran, and adding 0.01 mL N, N, N', N", N"-pentamethyldiethylenetriamine and 6 mg of cuprous bromide were used as catalysts, and the reaction was stirred for 48 hours under a nitrogen atmosphere. In this step, the sulfhydryl group at one end of the azide thiol forms a gold-sulfur bond with the surface of the ferroferric oxide/gold complex, and the azide group at the other end forms a click reaction with the alkyne group in the alkynyl graphene oxide. Covalently linked, after completion of the reaction, the product is dissolved in dimethylformamide or tetrahydrofuran, and the product is collected by filtration to obtain.
性能测试Performance Testing
分别根据相关测试要求，将实施例1制备获得的石墨烯与四氧化三铁@金复合材料制备成浓度梯度为0mmoL/L、0.1mmoL/L、0.2mmoL/L、0.4mmoL/L、0.8mmoL/L及1mmoL/L的G-Fe3O4@Au纳米粒子溶液，应用在核磁成像、光声成像和微波热声成像中，浓度-信号响应曲线分别见图2、图3和图4。According to the relevant test requirements, the graphene prepared in Example 1 and the triiron tetroxide @gold composite material were prepared to have a concentration gradient of 0 mmoL/L, 0.1 mmoL/L, 0.2 mmoL/L, 0.4 mmoL/L, and 0.8 mmoL. /L and 1mmoL/L G-Fe 3 O 4 @Au nanoparticle solution, used in nuclear magnetic imaging, photoacoustic imaging and microwave thermoacoustic imaging, the concentration-signal response curves are shown in Figure 2, Figure 3 and Figure 4, respectively.
由图2可知，在相同[Fe]浓度下，G-Fe3O4@Au纳米粒子的T2序列核磁图像随G-Fe3O4@Au的浓度增加响应信号的颜色逐渐加深。It can be seen from Fig. 2 that at the same [Fe] concentration, the nuclear magnetic image of the T2 sequence of the G-Fe 3 O 4 @Au nanoparticles gradually increases with the concentration of the G-Fe 3 O 4 @Au.
由图3可知，光声信号响应强度与G-Fe3O4@Au的浓度增加而逐渐增大，呈正相关。It can be seen from Fig. 3 that the response intensity of the photoacoustic signal gradually increases with the concentration of G-Fe 3 O 4 @Au, and is positively correlated.
由图4可知，微波热声信号随G-Fe3O4@Au中的[Fe]浓度的增加而增加，整体上G-Fe3O4@Au的热声信号与G-Fe3O4@Au中的[Fe]浓度呈线性相关。From Figure 4, a microwave signal with thermoacoustic increasing concentrations of G-Fe 3 O 4 @Au of [Fe] is increased, the overall G-Fe 3 O 4 @Au thermoacoustic signal G-Fe 3 O 4 The [Fe] concentration in @Au is linearly related.
根据X光成像中的相关测试要求，将实施例1制备获得的石墨烯与四氧化三铁@金复合材料制备成1mg/mL、2mg/mL、4mg/mL及8mg/mL浓度梯度依次对应附图中成像标记号4、3、2和1，测试结果见图5。由图5可知，在X光成像中，X光成像图的颜色深度随G-Fe3O4@Au的质量浓度的增加而加深。According to the relevant test requirements in X-ray imaging, the graphene prepared in Example 1 and the ferroferric oxide @金 composite material were prepared to have a concentration gradient of 1 mg/mL, 2 mg/mL, 4 mg/mL and 8 mg/mL, respectively. In the figure, the imaging marks No. 4, 3, 2 and 1 are shown in Fig. 5. As can be seen from Fig. 5, in X-ray imaging, the color depth of the X-ray image is deepened as the mass concentration of G-Fe 3 O 4 @Au increases.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权 利要求为准。 The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of protection of the patent of the present invention should be attached The requirements are subject to change.

Claims (10)

  1. 一种石墨烯与四氧化三铁@金复合材料的制备方法，其特征在于，包括如下步骤：A method for preparing graphene and ferroferric oxide@gold composite material, comprising the steps of:
    (1)构建叠氮化硫醇修饰的四氧化三铁@金复合体和炔基化的氧化石墨烯：(1) Construction of azidothiol-modified triiron tetroxide @gold composite and alkynylated graphene oxide:
    其中，所述叠氮化硫醇修饰的四氧化三铁@金复合体包括如下构建步骤：Wherein, the azide thiol-modified ferroferric oxide@gold composite comprises the following construction steps:
    将纳米四氧化三铁分散于还原剂溶液中，超声处理，加热至65℃～75℃，在搅拌条件下滴加氯金酸水溶液，反应后停止加热，再搅拌熟化反应，获得具有核壳结构的四氧化三铁@金复合体；Dispersing the nanometer ferroferric oxide in the reducing agent solution, sonicating, heating to 65 ° C ~ 75 ° C, adding chloroauric acid aqueous solution under stirring, stopping heating after the reaction, and stirring the ripening reaction to obtain a core-shell structure Ferric oxide @金复合体;
    将所述四氧化三铁@金复合体和叠氮化硫醇置于第一溶剂中，在40～45℃条件下和在保护气氛围中搅拌反应，用第二溶剂反复冲洗，获得所述叠氮化硫醇修饰的四氧化三铁@金复合体；The ferroferric oxide@gold composite and the azide thiol are placed in a first solvent, and the reaction is stirred at 40 to 45 ° C under a protective gas atmosphere, and repeatedly washed with a second solvent to obtain the Azidothiol-modified triiron tetroxide@gold composite;
    所述炔基化的氧化石墨烯包括如下构建步骤：The alkynylated graphene oxide comprises the following construction steps:
    在65～75℃条件下，将氧化石墨烯置于活化剂中进行活化反应，再加入炔丙醇继续反应20～28h，得到所述炔基化的氧化石墨烯；At 65-75 ° C, the graphene oxide is placed in an activator for activation reaction, and then propargyl alcohol is added to continue the reaction for 20-28 h to obtain the alkynylated graphene oxide;
    (2)构建石墨烯与四氧化三铁@金复合材料：(2) Construction of graphene and ferroferric oxide @金 composite materials:
    将步骤(1)构建的所述叠氮化硫醇修饰的四氧化三铁@金复合体和所述炔基化的氧化石墨烯溶解在第三溶剂中，加入催化剂，在保护气氛围中，搅拌反应，收集产物，即得。Dissolving the azide thiol-modified Fe3O4 gold complex and the alkynylated graphene oxide constructed in the step (1) in a third solvent, adding a catalyst, in a protective gas atmosphere, The reaction was stirred and the product was collected to give.
  2. 根据权利要求1所述的石墨烯与四氧化三铁@金复合材料的制备方法，其特征在于，在步骤(2)中，所述叠氮化硫醇修饰的四氧化三铁@金复合体和所述炔基化的氧化石墨烯的质量浓度比为30～50:30～50。The method for preparing a graphene and a ferroferric oxide@gold composite material according to claim 1, wherein in the step (2), the azide-sulfide-modified triiron tetroxide@gold composite The mass concentration ratio of the alkynylated graphene oxide is from 30 to 50:30 to 50.
  3. 根据权利要求2所述的石墨烯与四氧化三铁@金复合材料的制备方法，其特征在于，在步骤(2)中，所述第三溶剂为二甲基甲酰胺或四氢呋喃，所述催化剂为N,N,N',N″,N″-五甲基二亚乙基三胺和溴化亚铜的混合物。The method for preparing a graphene and a ferroferric oxide@gold composite according to claim 2, wherein in the step (2), the third solvent is dimethylformamide or tetrahydrofuran, the catalyst It is a mixture of N, N, N', N", N"-pentamethyldiethylenetriamine and cuprous bromide.
  4. 根据权利要求1至3中任一项所述的石墨烯与四氧化三铁@金复合材料的制备方法，其特征在于，在步骤(1)中，所述叠氮化硫醇中碳原子的个数为N，6＜N＜15；所述四氧化三铁@金复合体和叠氮化硫醇的质量比为100:0.4～2。The method for producing a graphene and a ferroferric oxide@gold composite according to any one of claims 1 to 3, wherein in the step (1), the carbon atom in the azide thiol The number is N, 6 < N < 15; the mass ratio of the triiron tetroxide @ gold complex to the azide thiol is 100: 0.4 to 2.
  5. 根据权利要求4所述的石墨烯与四氧化三铁@金复合材料的制备方法， 其特征在于，在步骤(1)中，所述活化剂为二氯亚砜，所述氧化石墨烯在所述二氯亚砜中的活化反应时间为20～28h。The method for preparing graphene and ferroferric oxide@gold composite material according to claim 4, It is characterized in that in the step (1), the activator is thionyl chloride, and the activation reaction time of the graphene oxide in the thionyl chloride is 20 to 28 h.
  6. 根据权利要求1至3中任一项所述的石墨烯与四氧化三铁@金复合材料的制备方法，其特征在于，在步骤(1)中，所述第一溶剂为甲苯；所述第二溶剂为非极性溶剂；所述四氧化三铁@金复合体和叠氮化硫醇的反应时间为45～55h。The method for preparing a graphene and a ferroferric oxide@gold composite according to any one of claims 1 to 3, wherein in the step (1), the first solvent is toluene; The disolvent is a non-polar solvent; the reaction time of the triiron tetroxide/gold complex and the azide thiol is 45 to 55 h.
  7. 根据权利要求1至3中任一项所述的石墨烯与四氧化三铁@金复合材料的制备方法，其特征在于，在步骤(1)中，所述纳米四氧化三铁包括如下制备步骤：将1.8～2.2g的FeCl3·6H2O溶解在100±5mL的蒸馏水中，在氮气氛围中和搅拌条件下加入0.8～1.2g的FeCl2·4H2O，再滴加氨水或氢氧化钠溶液至反应液的pH升至8.8～9.5，再加热至80℃～90℃条件下反应20～30min，经磁性分离，即得所述纳米四氧化三铁；The method for preparing a graphene and a ferroferric oxide@gold composite according to any one of claims 1 to 3, wherein in the step (1), the nano-ferric oxide comprises the following preparation steps : Dissolve 1.8 to 2.2 g of FeCl 3 ·6H 2 O in 100±5 mL of distilled water, add 0.8-1.2 g of FeCl 2 ·4H 2 O under stirring in a nitrogen atmosphere, and add dropwise ammonia or hydroxide. The pH of the sodium solution to the reaction solution is raised to 8.8 to 9.5, and then heated to 80 ° C to 90 ° C for 20 to 30 minutes, and magnetic separation, the nanometer ferroferric oxide is obtained;
    在所述叠氮化硫醇修饰的四氧化三铁@金复合体的构建步骤中，所述还原剂为柠檬酸钠，所述柠檬酸钠的质量浓度为1～3mg/mL，体积为100±5mL；所述氯金酸水溶液的质量浓度为8～12mg/mL，加入体积为8～12mL。In the step of constructing the azide thiol-modified triiron tetroxide@gold composite, the reducing agent is sodium citrate, and the sodium citrate has a mass concentration of 1-3 mg/mL and a volume of 100. ±5 mL; the mass concentration of the aqueous chloroauric acid solution is 8 to 12 mg/mL, and the volume of addition is 8 to 12 mL.
  8. 根据权利要求1至3中任一项所述的石墨烯与四氧化三铁@金复合材料的制备方法，其特征在于，在步骤(1)中，所述氧化石墨烯的制备过程包括如下步骤：The method for preparing a graphene and a ferroferric oxide@gold composite material according to any one of claims 1 to 3, wherein in the step (1), the preparation process of the graphene oxide comprises the following steps :
    在冰浴条件下，向0.4～0.6g天然石墨及0.5～0.6g硝酸钠的混合体系中加入13～17mL浓硫酸，再加入1.3～1.7g高锰酸钾，并保持反应体系的温度不高于5℃；In an ice bath, add 13 to 17 mL of concentrated sulfuric acid to a mixed system of 0.4 to 0.6 g of natural graphite and 0.5 to 0.6 g of sodium nitrate, and then add 1.3 to 1.7 g of potassium permanganate, and keep the temperature of the reaction system low. At 5 ° C;
    加料完毕后，将上述反应体系加热至28～32℃条件下反应55～65min，再向该反应体系加入15～25mL去离子水，升温至90～99℃，继续反应13～17min，再加入65～75mL去离子水，再滴加2.0～3.0mL双氧水，除去过量的高锰酸钾，此时溶液为亮黄色，静置一天，去上清液，用去离子水洗涤下层黄色固体，反复冲洗至上清液中无酸性和硫酸根离子，冷冻干燥，即得所述氧化石墨烯。After the addition is completed, the reaction system is heated to 28 to 32 ° C for 55 to 65 minutes, and then 15 to 25 mL of deionized water is added to the reaction system, and the temperature is raised to 90 to 99 ° C, and the reaction is continued for 13 to 17 minutes, and then 65 is added. ~75mL deionized water, add 2.0 ~ 3.0mL hydrogen peroxide, remove excess potassium permanganate, the solution is bright yellow, let stand for one day, remove the supernatant, wash the lower yellow solid with deionized water, rinse repeatedly There is no acid and sulfate ion in the supernatant, and freeze-drying, that is, the graphene oxide is obtained.
  9. 一种由权利要求1至8中任一项所述的石墨烯与四氧化三铁@金复合材料的制备方法制备获得的石墨烯与四氧化三铁@金复合材料。 A graphene and a ferroferric oxide@gold composite material prepared by the method for preparing a graphene and a ferroferric oxide@gold composite material according to any one of claims 1 to 8.
  10. 根据权利要求9所述的石墨烯与四氧化三铁@金复合材料在核磁成像、微波热声成像、光声成像、X光成像中的应用。 The use of graphene and ferroferric oxide@gold composite material according to claim 9 in nuclear magnetic imaging, microwave thermoacoustic imaging, photoacoustic imaging, and X-ray imaging.
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