CN111467563B - Synthetic method of RGO/MWCNT/HA/Fe3O4 composite material - Google Patents

Synthetic method of RGO/MWCNT/HA/Fe3O4 composite material Download PDF

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CN111467563B
CN111467563B CN202010150919.4A CN202010150919A CN111467563B CN 111467563 B CN111467563 B CN 111467563B CN 202010150919 A CN202010150919 A CN 202010150919A CN 111467563 B CN111467563 B CN 111467563B
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rgo
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CN111467563A (en
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卢晓英
魏立恒
李冕
卢怡
宋华军
雷志豪
翁杰
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Southwest Jiaotong University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/08—Carbon ; Graphite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P19/00—Drugs for skeletal disorders
    • A61P19/08—Drugs for skeletal disorders for bone diseases, e.g. rachitism, Paget's disease
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602—Type of release, e.g. controlled, sustained, slow
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses RGO/CNT/HA/Fe3O4The synthesis method of the composite material comprises the following steps: s1, dividing a double-ion surfactant into a reactant I and a reactant II; s2, mixing and stirring the reactant I and the solvent I uniformly to obtain a surfactant solution; s3, mixing and grinding the multi-walled nanotubes and the reactant II, and adding the mixture into a surfactant solution to obtain a CNT dispersion solution; s4, taking oxidized graphene and a solvent II, and uniformly stirring to obtain a mixed solution I; s5, adding the CNT dispersion liquid into the mixed liquid I, and performing electrostatic self-assembly reaction to obtain a reaction liquid I; s6, adding NH4H2PO4The solution is added dropwise to Ca (NO)3)2Obtaining a mixed solution II; s7, sequentially adding Fe (NH)4)2(SO4)2Adding the solution, the mixed solution II, a urea solution and an alkaline solution into the reaction solution I to obtain a reaction solution II with the pH value of 11; s8, adding the disodium ethylene diamine tetraacetate solution, polyethylene glycol 200 and hydrazine hydrate into the reaction liquid II to obtain a reaction liquid III; s9, carrying out hydrothermal reaction on the reaction liquid III to obtain an intermediate product; s10, carrying out suction filtration, washing and drying treatment on the intermediate product to obtain RGO/CNT/HA/Fe3O4A composite material.

Description

RGO/MWCNT/HA/Fe3O4Synthesis method of composite material
Technical Field
The invention relates to the technical field of composite material synthesis, in particular to RGO/MWCNT/HA/Fe3O4A method for synthesizing a composite material.
Background
Carbon nanotubes (A), (B), (C)Carbon nanotubes, abbreviated as CNTs), are an allotrope of Carbon, as are diamond, graphite, and fullerenes. It is a tubular carbon molecule, with each carbon atom on the tube adopting sp2And hybridization is carried out, and carbon-carbon sigma bonds are combined with each other to form a honeycomb structure consisting of hexagons as the framework of the carbon nano tube.
Reduced Graphene Oxide (RGO) is Graphene that is chemically oxidized by a strong oxidant and then Reduced.
RGO and CNT are commonly used to synthesize RGO/CNT composites, where RGO/CNT is the host of a three-dimensional scaffold with good electrical, thermal and mechanical properties. However, the composite materials synthesized in the prior art are only suitable for the fields of hydrogen evolution, batteries, energy sources, electricity and the like, and an RGO/CNT composite material suitable for the medical field and a synthesis method thereof do not appear yet.
Therefore, there is a need for an RGO/CNT composite material and a method for synthesizing the same, so that the RGO/CNT composite material has good magnetic and biological activities, and thus can be applied to medical fields such as scaffolds for bone tissue engineering, magnetocaloric therapy, drug loading and sustained release.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an RGO/MWCNT/HA/Fe3O4The composite material has excellent magnetism and bioactivity, and is suitable for use in bone tissue engineering rack, magnetic heat treatment, medicine loading, slow releasing and other medical fields.
The purpose of the invention is realized by the following technical scheme: RGO/MWCNT/HA/Fe3O4The synthesis method of the composite material comprises the following steps:
s1, dividing a double-ion surfactant into a reactant I and a reactant II;
s2, mixing and stirring the reactant I and the solvent I uniformly to obtain a surfactant solution;
s3, mixing and grinding a multi-walled carbon nanotube (MWCNT) and the reactant II, and adding the mixture into the surfactant solution to obtain MWCNT dispersion liquid for later use;
s4, taking graphene oxide and a solvent II to mix and stir uniformly to obtain a mixed solution I;
s5, adding the MWCNT dispersion liquid into the mixed liquid I, and performing electrostatic self-assembly reaction to obtain a reaction liquid I;
wherein, a GO/MWCNT network structure is formed in the reaction liquid I, at the moment, the cation head of the double-ion surfactant is exposed in the solution and is combined with the negatively charged functional group (hydroxyl, carboxyl and the like) on the GO surface, and the anion head is protected and is not used because the solution environment of the reaction liquid I is acidic or neutral;
s6, adding NH4H2PO4The solution is added dropwise to Ca (NO)3)2Obtaining a mixed solution II;
s7, sequentially adding Fe (NH)4)2(SO4)2Adding a solution, the mixed solution II, a urea solution and an alkaline solution into the reaction solution I to obtain a reaction solution II with the pH of 11;
wherein, the urea is used for continuously providing OH in the hydrothermal process-This is the synthesis of HA and Fe3O4The key of (1); the alkaline solution is used for adjusting the pH value of the solution to be alkaline so as to synthesize HA and Fe3O4Providing an alkaline environment, wherein the anionic head of the zwitterionic surfactant is exposed to the solution and continuously attracts positively charged ions, such as Ca, in the solution2+、Fe2+(ii) a From this point onwards, MWCNT and Ca2+、Fe2+Are assembled on the surface of GO sheet layer, thus leading HA and Fe3O4Can deposit on the RGO surface during the hydrothermal reaction of step S9, so that the material has magnetism and better bioactivity;
s8, mixing ethylene diamine tetraacetic acid, polyethylene glycol 200, hydrazine hydrate and the reaction liquid II to obtain a reaction liquid III; the dosage of the disodium ethylene diamine tetraacetate is 2-4 g, the dosage of the polyethylene glycol 200 is 1-5 mL, and the dosage of the hydrazine hydrate is 5-10 mL;
s9, carrying out hydrothermal reaction on the reaction liquid III to obtain an intermediate product;
s10, carrying out vacuum filtration, washing and vacuum drying on the intermediate product to obtain the RGO/MWCNT/HA/Fe3O4A composite material.
Further, the double-ion surfactant is trisulfopropyl tetradecyl dimethyl betaine.
Through the technical scheme, the double-ion surfactant can enable MWCNT to be dispersed more uniformly, and meanwhile, the protected anion head of the double-ion surfactant provides possibility for attracting more positively charged ions on the surface of GO or the surface of MWCNT subsequently, and also provides possibility for the multi-functionalization of the composite material.
Further, the mass ratio of the double-ion surfactant to the multi-wall carbon nano tube is 2-4: 1.
Furthermore, the solvent I and the solvent II are both deionized water.
Further, in S5, the time of the electrostatic self-assembly reaction is 2-4 h.
Further, in S5, the flow rate at the time of slow addition was 60 rpm/min.
Further, in the mixed solution II, Ca is calculated by mol2+:PO4 3- - - (1.67: 1); by mass, Fe2+:Ca2+＝1:2～4， GO/MWCNT:Ca2+/Fe2+＝1:2～4。
Wherein, Ca2+And PO4 3-The molar ratio of (a) to (b) is the conventional ratio for synthesizing HA.
By the technical scheme, the Fe2+The more the gain, the more the magnetic properties of the resulting material; ca2+The more the yield, the better the bioactivity of the obtained material; ca2+/Fe2+The more the overall yield, the more it will lay on the surface of the final synthetic RGO; by the pair of Fe2+With Ca2+The mass ratio of (A) to (B) is limited, so that HA and Fe are added3O4Effect as a filler for the inner space of RGO/MWCNT three-dimensional composite material, and as can be confirmed from FIG. 1, HA and Fe3O4The surface of the RGO has been flooded.
Further, in S7, the alkaline solution includes a NaOH solution.
Further, the mass ratio of the urea to the graphene oxide to the multi-walled carbon nano tubes is 15-30: 3: 1.
Further, the temperature of the hydrothermal reaction is 120 ℃, and the time is 10-24 hours.
The invention has the beneficial effects that:
1. RGO/MWCNT/HA/Fe of the invention3O4The composite material synthesis method can enable MWCNT to be dispersed more uniformly by using the dual-ion surfactant; meanwhile, the protected anion head in the double-ion surfactant also provides possibility for attracting more positively charged ions on the GO surface or MWCNT surface subsequently, and also provides possibility for the multifunctionalization of the composite material.
2. RGO/MWCNT/HA/Fe of the invention3O4The composite material is synthesized by adopting a one-step hydrothermal method to synthesize RGO/MWCNT/HA/Fe3O4The composite material and the method are simple, and the three-dimensional RGO/MWCNT composite material has better bioactivity and biocompatibility and certain magnetism, so that the three-dimensional RGO/MWCNT composite material can be well applied to medical fields of bone tissue engineering scaffolds, drug loading, slow release and the like, and the effect of expanding the application field of the RGO/MWCNT composite material is achieved.
Drawings
FIGS. 1-2 show an RGO/MWCNT/HA/Fe of the present invention3O4SEM images of the composite;
FIG. 3 shows an RGO/MWCNT/HA/Fe of the present invention3O4XRD pattern of the composite;
FIG. 4 shows an RGO/MWCNT/HA/Fe of the present invention3O4M-H curve of the composite.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
Example 1
RGO/MWCNT/HA/Fe3O4The synthesis method of the composite material comprises the following steps:
s1, weighing 200mg of a double-ion surfactant (trisulfopropyl tetradecyl dimethyl betaine) and equally dividing into a reactant I and a reactant II;
s2, dissolving the reactant I in 400mL of deionized water, and magnetically stirring uniformly to obtain a surfactant solution;
s3, mixing and grinding the reactant II and 50mg of MWCNT (multi-walled carbon nanotube), and then adding the mixture into the surfactant solution to obtain MWCNT dispersion liquid for later use;
s4, dissolving 150mg of GO in 300mL of deionized water, and uniformly stirring by magnetic force to obtain a mixed solution I;
s5, slowly adding the MWCNT dispersion liquid into the mixed liquid I at the speed of 60rpm/min through a constant flow pump, after all the MWCNT dispersion liquid is added, carrying out electrostatic self-assembly reaction for 3 hours, and obtaining a reaction liquid I after the MWCNT is uniformly dispersed on the surface of GO;
s6-1, preparing and synthesizing HA and Fe3O4Is (GO/MWCNT: Ca in terms of mass ratio)2+/Fe2+1: 4): 2801 mg ferrous ammonium sulfate hexahydrate (NH) was weighed4)2Fe(SO4)2·6H2Preparing O into 20mL solution; 1180.75mg of calcium nitrate tetrahydrate Ca (NO) are weighed out3)2·4H2Preparing O into 10mL solution; weighing 446.77mg of ammonium dihydrogen phosphate NH4H2PO4Preparing 10mL solution; weighing 2g of urea to prepare 20mL of solution;
s6-2, adding NH4H2PO4The solution was slowly added dropwise to Ca (NO) in magnetic stirring3)2Obtaining a mixed solution II;
s7, sequentially adding Fe (NH)4)2(SO4)2Slowly dripping the solution, the mixed solution II, the urea solution and the NaOH solution into the reaction solution I at a speed of 60rpm/min by a constant flow pump to obtain a reaction solution II with the pH value of 11;
s8-1, weighing 3g of disodium ethylene diamine tetraacetate to prepare 10mL of solution;
s8-2, mixing the ethylene diamine tetraacetic acid disodium solution, 1mL of polyethylene glycol 200, 10mL of hydrazine hydrate and the reaction liquid II to obtain a reaction liquid III;
s9, transferring the reaction liquid III to a hydrothermal reaction kettle, and keeping the reaction liquid III at the temperature of 120 ℃ for 10 hours to obtain an intermediate product;
s10, carrying out vacuum filtration on the intermediate product, repeatedly washing the intermediate product by using deionized water and absolute ethyl alcohol, and drying the intermediate product in vacuum to obtain RGO/MWCNT/HA/Fe3O4A composite material.
Example 2
RGO/MWCNT/HA/Fe3O4The synthesis method of the composite material comprises the following steps:
s1, weighing 100mg of a double-ion surfactant (trisulfopropyl tetradecyl dimethyl betaine) and equally dividing into a reactant I and a reactant II;
s2, dissolving the reactant I in 200mL of deionized water, and magnetically stirring uniformly to obtain a surfactant solution;
s3, mixing and grinding the reactant II and 50mg of MWCNT (multi-walled carbon nanotube), and then adding the mixture into the surfactant solution to obtain MWCNT dispersion liquid for later use;
s4, dissolving 150mg of GO in 300mL of deionized water, and uniformly stirring by magnetic force to obtain a mixed solution I;
s5, slowly adding the MWCNT dispersion liquid into the mixed liquid I at the speed of 60rpm/min through a constant flow pump, after all the MWCNT dispersion liquid is added, carrying out electrostatic self-assembly reaction for 2 hours, and obtaining a reaction liquid I after the MWCNT is uniformly dispersed on the surface of GO;
s6-1, preparing and synthesizing HA and Fe3O4Is (GO/MWCNT: Ca in terms of mass ratio)2+/Fe2+1: 3): 3733.24mg of ferrous ammonium sulfate hexahydrate (NH) were weighed4)2Fe(SO4)2·6H2Preparing O into 20mL solution; weighing 1573mg calcium nitrate tetrahydrate Ca (NO)3)2·4H2Preparing O into 10mL solution; weighing 526.92mg of ammonium dihydrogen phosphate NH4H2PO4Preparing 10mL solution; weighing 1g of urea to prepare 20mL of solution;
s6-2, adding NH4H2PO4The solution is slowly dripped into Ca in magnetic stirring(NO3)2Obtaining a mixed solution II;
s7, sequentially adding Fe (NH)4)2(SO4)2Slowly dripping the solution, the mixed solution II, the urea solution and the NaOH solution into the reaction solution I at a speed of 60rpm/min by a constant flow pump to obtain a reaction solution II with the pH value of 11;
s8-1, weighing 2g of disodium ethylene diamine tetraacetate to prepare 10mL of solution;
s8-2, mixing the ethylene diamine tetraacetic acid disodium solution, 3mL of polyethylene glycol 200, 5mL of hydrazine hydrate and the reaction liquid II to obtain a reaction liquid III;
s9, transferring the reaction liquid III to a hydrothermal reaction kettle, and keeping the reaction liquid III at the temperature of 120 ℃ for 16 hours to obtain an intermediate product;
s10, carrying out vacuum filtration on the intermediate product, repeatedly washing the intermediate product by using deionized water and absolute ethyl alcohol, and drying the intermediate product in vacuum to obtain RGO/MWCNT/HA/Fe3O4A composite material.
Example 3
RGO/MWCNT/HA/Fe3O4The synthesis method of the composite material comprises the following steps:
s1, weighing 150mg of a diionic surfactant (trisulfopropyl tetradecyl dimethyl betaine) and equally dividing into a reactant I and a reactant II;
s2, dissolving the reactant I in 300mL of deionized water, and magnetically stirring uniformly to obtain a surfactant solution;
s3, mixing and grinding the reactant II and 50mg of MWCNT (multi-walled carbon nanotube), and then adding the mixture into the surfactant solution to obtain MWCNT dispersion liquid for later use;
s4, dissolving 150mg of GO in 300mL of deionized water, and uniformly stirring by magnetic force to obtain a mixed solution I;
s5, slowly adding the MWCNT dispersion liquid into the mixed liquid I at the speed of 60rpm/min through a constant flow pump, after all the MWCNT dispersion liquid is added, carrying out electrostatic self-assembly reaction for 4 hours, and obtaining a reaction liquid I after the MWCNT is uniformly dispersed on the surface of GO;
s6-1, preparing and synthesizing HA and Fe3O4Is (GO/MWCNT: Ca in terms of mass ratio)2+/Fe2+1: 2): 1866.62mg of ferrous ammonium sulfate hexahydrate (NH) were weighed4)2Fe(SO4)2·6H2Preparing O into 20mL solution; 786.6mg of calcium nitrate tetrahydrate Ca (NO) are weighed out3)2·4H2Preparing O into 10mL solution; weighing 263.46mg of ammonium dihydrogen phosphate NH4H2PO4Preparing 10mL solution; weighing 1.5g of urea to prepare 20mL of solution;
s6-2, adding NH4H2PO4The solution was slowly added dropwise to Ca (NO) in magnetic stirring3)2Obtaining a mixed solution II;
s7, sequentially adding Fe (NH)4)2(SO4)2Slowly dripping the solution, the mixed solution II, the urea solution and the NaOH solution into the reaction solution I at a speed of 60rpm/min by a constant flow pump to obtain a reaction solution II with the pH value of 11;
s8-1, weighing 4g of disodium ethylene diamine tetraacetate to prepare 10mL of solution;
s8-2, mixing the ethylene diamine tetraacetic acid disodium solution, 5mL of polyethylene glycol 200, 7.5mL of hydrazine hydrate and the reaction liquid II to obtain a reaction liquid III;
s9, transferring the reaction liquid III to a hydrothermal reaction kettle, and keeping the reaction liquid III at the temperature of 120 ℃ for 24 hours to obtain an intermediate product;
s10, carrying out vacuum filtration on the intermediate product, repeatedly washing the intermediate product by using deionized water and absolute ethyl alcohol, and drying the intermediate product in vacuum to obtain RGO/MWCNT/HA/Fe3O4A composite material.
Test effects
To verify the RGO/MWCNT/HA/Fe of the present invention3O4The morphology and the performance of the composite material are respectively subjected to electron microscope scanning, X-ray diffraction test and magnetic test.
As can be seen from FIGS. 1-2, many short rod-like materials are finally compounded on the surface of RGO. As can be seen from FIG. 3, the resulting composite contained Fe3O4And hydroxyapatite. As can be seen from fig. 4, the obtained composite material has certain magnetism, and the magnetism is an attribute beneficial to bone repair and also an attribute influencing drug loading and slow release; at the same time, it is electrically conductive1.3S/cm, and a specific surface area of 60m2Around/g, there is still a large space available for loading the drug and there is a certain conductivity.
In conclusion, the RGO/MWCNT/HA/Fe of the present invention3O4The composite material has good magnetism and bioactivity, so that the composite material can be suitable for medical fields of bone tissue engineering scaffolds, magnetic-thermal therapy, drug loading, slow release and the like.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. RGO/MWCNT/HA/Fe3O4The method for synthesizing the composite material is characterized by comprising the following steps of:
s1, dividing a double-ion surfactant into a reactant I and a reactant II;
s2, mixing and stirring the reactant I and the solvent I uniformly to obtain a surfactant solution;
s3, mixing and grinding a multi-walled carbon nanotube (MWCNT) and the reactant II, and adding the mixture into the surfactant solution to obtain MWCNT dispersion liquid for later use;
s4, taking graphene oxide and a solvent II to mix and stir uniformly to obtain a mixed solution I;
s5, slowly adding the MWCNT dispersion liquid into the mixed liquid I, and performing electrostatic self-assembly reaction to obtain a reaction liquid I;
s6, adding NH4H2PO4The solution is added dropwise to Ca (NO)3)2Obtaining a mixed solution II;
s7, sequentially adding Fe (NH)4)2(SO4)2Solution, the mixed solution II and urea solutionAdding an alkaline solution into the reaction solution I to obtain a reaction solution II with the pH of 11;
s8, sequentially adding an ethylene diamine tetraacetic acid disodium solution, polyethylene glycol 200 and hydrazine hydrate into the reaction liquid II to obtain a reaction liquid III;
s9, carrying out hydrothermal reaction on the reaction liquid III to obtain an intermediate product;
s10, carrying out vacuum filtration, washing and vacuum drying on the intermediate product to obtain the RGO/MWCNT/HA/Fe3O4A composite material.
2. An RGO/MWCNT/HA/Fe according to claim 13O4The synthesis method of the composite material is characterized in that the double-ion surfactant is trisulfopropyl tetradecyl dimethyl betaine.
3. An RGO/MWCNT/HA/Fe according to claim 1 or 23O4The synthesis method of the composite material is characterized in that the mass ratio of the double-ion surfactant to the multi-wall carbon nano tube is 2-4: 1.
4. An RGO/MWCNT/HA/Fe according to claim 13O4The synthesis method of the composite material is characterized in that the solvent I and the solvent II are both deionized water.
5. An RGO/MWCNT/HA/Fe according to claim 13O4The synthetic method of the composite material is characterized in that in S5, the time of the electrostatic self-assembly reaction is 2-4 h.
6. An RGO/MWCNT/HA/Fe according to claim 13O4A method for synthesizing a composite material, wherein in S5, the flow rate at the time of slow addition is 60 rpm/min.
7. An RGO/MWCNT/HA/Fe according to claim 13O4Method for synthesizing composite material, and method for synthesizing composite materialCharacterized in that in the mixed solution II, Ca is calculated by mol2+:PO4 3-1.67: 1; by mass, Fe2+:Ca2+＝1:2～4，GO/MWCNT:Ca2+/Fe2+＝1:2～4。
8. An RGO/MWCNT/HA/Fe according to claim 13O4The method for synthesizing a composite material is characterized in that, in S7, the alkaline solution comprises NaOH solution.
9. An RGO/MWCNT/HA/Fe according to claim 13O4The synthesis method of the composite material is characterized in that the mass ratio of the urea to the graphene oxide to the multi-walled carbon nano-tubes is 15-30: 3: 1.
10. An RGO/MWCNT/HA/Fe according to claim 13O4The synthesis method of the composite material is characterized in that the temperature of the hydrothermal reaction is 120 ℃ and the time is 10-24 h.
CN202010150919.4A 2020-03-06 2020-03-06 Synthetic method of RGO/MWCNT/HA/Fe3O4 composite material Expired - Fee Related CN111467563B (en)

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