CN107537438B - Graphene-coated magnetic composite nano material and preparation method and application thereof - Google Patents
Graphene-coated magnetic composite nano material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene-coated magnetic composite nano material and a preparation method and application thereof, wherein the magnetic composite nano material is a core-shell structure which takes graphene as a shell and gold-cobalt alloy as a core, and the graphene is directly coated on the surface of the gold-cobalt alloy; the magnetic composite nano material is granular and has a particle size of 20-40 nm. The preparation method is simple, the cost is low, the controllability is strong, and the prepared MACGs composite nanoparticles have good uniformity and stable properties.
Description
Technical Field
The invention relates to a graphene-coated magnetic composite nano material, and a preparation method and application thereof, and belongs to the technical field of novel magnetic composite nano materials.
Background
The composite nano material is a popular research subject at present, and has excellent characteristics of multifunction, harmony, stability and the like, so that the composite nano material has very wide application in the fields of optics, biomedicine, environmental science, materials, catalysis, energy and the like. Compared with single-component nano materials, the multi-component composite nano material has more excellent properties by regulating the composition or the structure of the multi-component composite nano material, so that the application potential of the multi-component composite nano material in various fields is expanded. Recently, the magnetic composite nano material has attracted wide attention due to its magnetic property and stability, so the preparation of the magnetic composite nano material with uniform size, stability, easy modification and good biocompatibility has very important application value in the fields of biological enrichment, separation and other research.
One current method for preparing magnetic composite nanomaterials is to incorporate Fe3O4The magnetic core-shell nano material is formed by covalent bonding with AuNPs, and the other method is to use Fe3O4The surface of the nano-particle is wrapped with a gold shell layer by a gold reduction method, and the two methods have the defects of complex synthesis method, non-uniform size and material stabilityAnd poor biocompatibility, which limits its application in the field of bioanalysis.
Disclosure of Invention
The technical problem solved by the invention is that the existing synthesis method of the magnetic composite nano material is complex, the size is not uniform, and in addition, the stability and the biocompatibility of the material are not good, so that the application of the magnetic composite nano material in the field of biological analysis is limited.
The invention provides a graphene-coated magnetic composite nano material, which is a core-shell structure consisting of a shell made of graphene and a core made of a gold-cobalt alloy, wherein the graphene is directly coated on the surface of the gold-cobalt alloy; the magnetic composite nano material is granular and has a particle size of 20-40 nm.
Preferably, the number of graphene layers on the surface of the gold-cobalt alloy is 3-4.
Preferably, the gold to cobalt molar ratio of the gold-cobalt alloy is from 8:1 to 1: 1.
Preferably, the gold to cobalt molar ratio of the gold-cobalt alloy is from 7:1 to 5: 1.
The invention also provides a preparation method of the graphene-coated magnetic composite nano material, which comprises the following steps:
(1) mixing SiO2Adding into methanol solution, and performing ultrasonic treatment for 1-2 hr to obtain solution A, wherein SiO is2The mass-volume ratio of the methanol to the methanol is 1:80-100, the mass unit is g, and the volume unit is mL; mixing Co (NO)3)2·6H2O and 5-20mg/mL HAuCl4Mixing the solutions to obtain a solution B; mixing 40-60 parts by volume of the solution A and 1 part by volume of the solution B, then carrying out ultrasonic treatment for 1-2 hours, removing methanol, and drying the obtained mixture;
(2) grinding the mixture dried in the step (1) into powder, and then adding into CH4The flow rate is 10-60cm2Igniting for 10-15min under the condition of gas flow of/mL, wherein the ignition temperature is 800-2And separating (preferably, magnetically separating) the obtained solid to obtain the magnetic composite nano-particles wrapped by the graphene.
Preferably, in the step (2), the mass-to-volume ratio of the powder to the HF solution is 0.75-0.85:25-30, the mass unit is g, the volume unit is mL, and the mass fraction of the HF solution is more than or equal to 40%. The mass fraction of the HF solution is 40-60%.
Preferably, the power of the ultrasonic treatment in the step (1) is 170-200 w.
Preferably, in the step (1), the molar ratio of Au to Co in the solution B is 10:1-1: 2.
Preferably, the magnetic composite nano-material coated by the graphene obtained in the step (2) is dispersed in an aqueous solution of polyethylene glycol octadecyl ether, preferably a saturated aqueous solution of polyethylene glycol octadecyl ether, so as to obtain a magnetic composite nano-particle solution coated by the graphene.
Preferably, the magnetic composite nano material obtained by the preparation method or the application of the magnetic composite nano material in biological imaging.
The invention develops a novel graphene-coated Magnetic composite nano Material (MACGs), the core of the material is composed of alloy formed by two metal elements of gold and cobalt, so that the material has the properties of magnetism and plasma, and in addition, the graphene uniformly coated on the surface of gold-cobalt nano particles enables the material to be more stable, easy to modify and good in biocompatibility. The gold nanoparticles in the MACGs composite nano material can be used as a Surface-Enhanced Raman Scattering (SERS) substrate for high-sensitivity detection of Raman signal molecules. Graphene coated on the surfaces of MACGs has unique Raman scattering peaks and can be used for SERS Raman imaging. In addition, the Magnetic property of the MACGs composite nano-material enables the MACGs composite nano-material to have good application potential in Magnetic Resonance Imaging (MRI) and Magnetic enrichment.
The method for synthesizing the MACGs composite nanomaterial is simple in operation steps, the synthesized material is uniform in size, and the graphene coated on the surface of the material improves the biocompatibility of the material, enables the surface of the material to be easier to modify, and has good application value in various fields.
Compared with the prior art, the invention has the beneficial effects that: the preparation method is simple, low in cost and strong in controllability. The prepared MACGs composite nanoparticles have good uniformity and stable properties. And the composite nano-particles have various properties, so that the composite nano-particles have good application prospects in the fields of Raman enhancement, magnetic resonance imaging, magnetic enrichment, biological detection under extreme conditions, two-photon fluorescence, computed tomography imaging and the like. The graphene uniformly coated on the surfaces of the MACGs nanoparticles enables the material to be more stable, easy to modify and good in biocompatibility. The gold nanoparticles in the MACGs composite nano material can be used as an SERS substrate for high-sensitivity detection of Raman signal molecules. Graphene coated on the surfaces of MACGs has unique Raman scattering peaks and can be used for SERS Raman imaging. In addition, the magnetic property of the MACGs composite nano material enables the MACGs composite nano material to have good application value in the aspects of MRI imaging and magnetic enrichment.
Drawings
FIG. 1 is a representation of MACGs nanoparticles made according to the present invention; wherein a) is a schematic diagram of MACGs, b) is an ultraviolet-visible absorption spectrum diagram of MACGs, c) and d) are transmission electron microscope diagrams of MACGs, the interpolation diagram in d) is a lattice fringe diagram of Au and Co alloy, and e) is a scanning transmission electron microscope diagram of MACGs (left: dark field imaging; the method comprises the following steps: au; and (3) right: co);
FIG. 2 is a Raman spectrum and Raman imaging of MACGs nanoparticles prepared in accordance with the present invention; wherein, a) is Raman spectrogram of MACGs, b) is Raman enhancement spectrogram of R6G, and c) is Raman imaging chart of nematodes (G peak imaging);
FIG. 3 is a graph of MRI imaging and enrichment effect of MACGs nanoparticles prepared according to the invention; a) t being MACGs2Relaxation values, b) MRI images of MACGs, c) signal change images of Raman signal molecules before and after enrichment with MACGs.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The preparation method of the magnetic composite nano material wrapped by the graphene comprises the following steps:
(1) 3.0 g of SiO are weighed2Adding the mixture into 240 mL of methanol solution for ultrasonic treatment of 1-2h, obtaining a solution A; 6.0 mg of Co (NO) are weighed out3)2· 6H2O and 5.0 mL of 10 mg/mL HAuCl4Mixing (the molar ratio of Au to Co is 6: 1) to obtain a solution B; mixing the solution A and the solution B, then carrying out ultrasonic treatment for 1-2h, removing methanol, and drying the obtained mixture at the temperature of 45-50 ℃; wherein, the ultrasonic treatment in the step (1) refers to ultrasonic treatment under 200 w;
(2) drying the mixture obtained in the step (1), grinding the mixture into powder, and adding CH4The flow rate is 10 cm2Firing for 13 min under the condition of a/mL airflow, wherein the firing temperature is 1000 ℃, cooling, mixing with an HF solution, and magnetically removing the HF solution to obtain graphene-coated magnetic composite nanoparticles; wherein the mass-volume ratio of the powder to the HF solution is 0.75-0.85:25-30, the mass unit is g, and the volume unit is mL.
Example 2
The preparation method of the magnetic composite nano material wrapped by the graphene comprises the following steps:
(1) 3.0 g of SiO are weighed2Adding the mixture into 240 mL of methanol solution for ultrasonic treatment for 1.5h to obtain solution A; 6.0 mg of Co (NO) are weighed out3)2· 6H2O and 5.0 mL of 10 mg/mL HAuCl4Mixing to obtain solution B; mixing the solution A and the solution B, then carrying out ultrasonic treatment for 1.5h, removing methanol, and drying the obtained mixture at the temperature of 45-50 ℃; the power of ultrasonic treatment is 200 w;
(2) drying the mixture obtained in the step (1), grinding the mixture into powder, and adding CH4The flow rate is 60cm2Firing for 13 min under the condition of a/mL airflow, wherein the firing temperature is 1000 ℃, cooling, mixing with an HF solution, and magnetically removing the HF solution to obtain graphene-coated magnetic composite nanoparticles; wherein the mass-volume ratio of the powder to the HF solution is 0.75-0.85:25-30, the mass unit is g, and the volume unit is mL.
(3) Mixing the graphene-coated magnetic composite nanoparticles collected in the step (2) with saturated C18PEG (polyethylene glycol stearyl ether, C)18H37(OCH2CH2)nOH, n is about100, purchased from SIGMA-ALDRICH, CAS No.: 9005-00-9) and mixing the water solutions according to the mass-volume ratio of 13.9-14.5:15-20, wherein the mass unit is mg and the volume unit is mu L, and carrying out ultrasonic treatment for 1-2h under the condition of 200w until the particles are completely dissolved, thereby obtaining the stable graphene-coated magnetic composite nano-material solution.
As can be seen from FIG. 1, the synthesized MACGs are uniform in size, about 30 nm in particle size (FIG. 1 c), 3-4 layers of graphene are uniformly coated on the surface of the particles (FIG. 1 d), and as can be seen from FIG. 1 e, the core of the MACGs is composed of an alloy of Au and Co. As can be seen from fig. 2, the MACGs surface-coated graphene has unique raman scattering peaks (D, G, 2D peaks) (fig. 2 a), and can be used for imaging of biological systems (nematodes) (fig. 2 c) by using the unique raman scattering peaks (G peaks), and furthermore, MACGs can also be used as a raman enhancement substrate for enhancement of raman signaling molecules (R6G) (fig. 2 b). As can be seen from FIG. 3, MACGs are a type T2Contrast agent (FIG. 3 a), FIG. 3b is a magnetic resonance image of the corresponding MACGs concentrations of FIG. 3 a, illustrating that the MACGs can be regarded as T2The contrast agent is used for magnetic resonance imaging in a biological system, and can be used for enrichment of biomolecules by utilizing the magnetism of MACGs, and FIG. 3 c shows that the Raman signal molecules at different concentrations are enhanced in Raman signal intensity under the enrichment action of MACGs. Through the analysis, the magnetic composite nano material coated by the graphene synthesized by the invention has the following advantages: 1. the synthesis steps are simple, the size is uniform, and the property is excellent; the MACGs nanoparticles can be used as a Raman enhancement substrate for high-sensitivity detection of Raman signal molecules; 3. the Raman scattering material also has unique Raman scattering property and can be used for SERS Raman imaging; 4. the MACGs nano material is T2Contrast agents, useful for MRI imaging; 5. the separation and enrichment of biomolecules can be realized by utilizing the magnetic property of the MACGs nano material under the condition of an external magnetic field. 6. In addition, the MACGs nanoparticles have good application prospects in the fields of two-photon fluorescence, computed tomography imaging and the like.
Example 3
The experimental procedure is the same as in example 1, with the difference that other CHs are considered4Flow rate (20, 30, 40, 50 c)m2/mL) on the morphology of the synthesized MACGs, and the experimental results show that the synthesized MACGs are not greatly influenced in the flow range of the methane to be investigated, so that the flow of the methane is preferably 40 cm at last2/mL。
Example 4
The experimental procedure was as in example 1, except that the flow rate of methane was 40 cm2/mL，Co(NO3)2· 6H2The mass of O is 20.3 mg, HAuCl4The volume of (10 mg/mL) is 2.9 mL (Au to Co molar ratio is 1: 1), under which the surface-coated graphene of the synthesized MACGs particles is not uniform, and a large amount of amorphous carbon is generated.
Claims (7)
1. A preparation method of a magnetic composite nano material wrapped by graphene is characterized by comprising the following steps:
(1) mixing SiO2Adding into methanol solution, and performing ultrasonic treatment for 1-2 hr to obtain solution A, wherein SiO is2The mass-volume ratio of the methanol to the methanol is 1:80-100, the mass unit is g, and the volume unit is mL; mixing Co (NO)3)2·6H2O and 5-20mg/mL HAuCl4Mixing the solutions to obtain a solution B; mixing 40-60 parts by volume of the solution A and 1 part by volume of the solution B, then carrying out ultrasonic treatment for 1-2 hours, removing methanol, and drying the obtained mixture;
(2) grinding the mixture dried in the step (1) into powder, and then adding into CH4The flow rate is 10-60cm2Burning for 10-15min under the condition of gas flow of/mL, wherein the burning temperature is 800-;
the magnetic composite nano material is a core-shell structure which takes graphene as a shell and gold-cobalt alloy as a core, and the graphene is directly wrapped on the surface of the gold-cobalt alloy; the magnetic composite nano material is granular, and the grain diameter is 20-40 nm;
the molar ratio of the gold to the cobalt in the gold-cobalt alloy is 7:1-5: 1.
2. The preparation method according to claim 1, wherein in the step (2), the mass-to-volume ratio of the powder to the HF solution is 0.75-0.85:25-30, the mass unit is g, the volume unit is mL, and the mass fraction of the HF solution is not less than 40.0%.
3. The method as claimed in claim 1, wherein the power of the ultrasonic treatment in step (1) is 170-200W.
4. The method according to claim 1, wherein in the step (1), the molar ratio of Au to Co in the solution B is 10:1 to 1: 2.
5. The preparation method according to claim 1, wherein the graphene-coated magnetic composite nano-material obtained in the step (2) is dispersed in an aqueous solution of polyethylene glycol octadecyl ether to obtain a graphene-coated magnetic composite nano-particle solution.
6. The preparation method according to claim 1, wherein the number of graphene layers on the surface of the gold-cobalt alloy is 3-4.
7. Use of the magnetic composite nanomaterial obtained by the preparation method according to any one of claims 1 to 6 in biological imaging.
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| CN111005091B (en) * | 2019-12-30 | 2022-05-03 | 西北工业大学 | Preparation method of high-stability flexible graphene/AuNPs SERS substrate composite fiber |
| CN113020590B (en) * | 2021-03-02 | 2022-04-19 | 湖南大学 | Graphene-coated cobalt-platinum composite nano material and preparation process and application thereof |
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