CN110648839B - Gold-magnetic composite microsphere with monodispersity and superparamagnetism and preparation method thereof - Google Patents
Gold-magnetic composite microsphere with monodispersity and superparamagnetism and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of gold-magnetic composite microspheres with monodispersity and superparamagnetism, which comprises the following steps: (1) adding ferric chloride and sodium acetate into 1, 2-propylene glycol, uniformly mixing to obtain a bright yellow mixed solution, heating to 90-110 ℃, and obtaining mesoporous Fe after the bright yellow mixed solution turns into ginger yellow3O4Carrying out solvothermal reaction on the precursor solution to obtain mesoporous Fe3O4(ii) a (2) Dissolving anhydrous sodium citrate in water, adding mesoporous Fe3O4Stirring the obtained mixed solution at room temperature to obtain the surface modified mesoporous Fe3O4A solution; (3) modifying the surface of the mesoporous Fe3O4And heating the solution, adding a chloroauric acid aqueous solution, separating out a precipitate after reaction, washing and drying to obtain the gold-magnetic composite microsphere. The nanometer Fe prepared by the invention3O4The Au composite material has good dispersibility in aqueous solution and has wide application prospect in the field of biomedicine.
Description
Technical Field
The invention belongs to the technical field of inorganic nano composite materials, and particularly relates to Fe with monodispersity and superparamagnetism3O4Au composite microspheres and a preparation method thereof.
Background
The nano composite material is characterized in that the dimension linearity of the material is in a nano level, and the nano composite material is generally composed of two or more nano materials according to a certain structure, so that the material obtains excellent comprehensive characteristics, and has the quantum size effect, the surface effect, the volume effect and the like which are unique to a single component, and also has the synergistic effect of a plurality of nano component structures. Due to its unique structure and composite function, the nanocomposite has gained a great deal of attention and application in the fields of electronics, optics, catalysis, biomedical technology, and the like.
The gold magnetic nano composite material is a common nano composite structure, and generally refers to a colloid material which is compounded by taking superparamagnetic ferroferric oxide and simple substance gold as main components and has a nano-scale particle size. According to the disuse of the two component composition modes, the gold-magnetic composite material is divided into a core-shell type, a dumbbell type, an assembly type, a multi-component mixed type and other types. The gold magnetic particles not only have unique magnetic properties of magnetic materials, but also have good biocompatibility, chemical stability and unique optical characteristics of colloidal gold, so that the gold magnetic particles are gradually developed into a novel material with wide application prospects, and have wide application in the fields of immunological detection, nucleic acid protein purification, enzyme immobilization, cell separation, drug targeting treatment and the like. However, gold magnetic particles themselves have excessive specific surface energy and low charge, and instability, aggregation and precipitation under physiological conditions are one of the challenges facing the application in the medical field.
At present, most of the preparation methods of gold magnetic nano composite materials are Fe3O4Adding reducing agent (hydroxylamine hydrochloride, sodium borohydride, sodium citrate) into the solution to react with chloroauric acid (HAuCl)4·4H2O) reduction, the reducing agent and chloroauric acid are carried out in solution, and the reduced gold is further mixed with Fe3O4Compounding to obtain the gold-magnetic composite particles. But Fe under boiling conditions during the preparation process3O4The solution is easy to oxidize so as to weaken the magnetism, more importantly, the growth process of the gold magnetic nano particles is easy to appear and is difficult to control, and the obtained composite material has poor dispersibility. Later, some researchers have chosen layer-by-layer assembly and seed crystal growth methods to synthesize gold magnetic particles, first prepared Fe3O4Surface modification is carried out to carry out positive charge, and then the colloidal gold particles with negative charge are loaded on Fe through electrostatic adsorption acting force3O4Surface, with this seed as the growth center, by controlling HAuCl4·4H2The flow rates of O and the reducing agent are adopted, so that the gold magnetic composite material is obtained, the Au shell of the particles prepared by the method is uniform, but the process is complicated, and the yield is not high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of gold-magnetic composite microspheres with monodispersity and superparamagnetism, which is simple and can be produced in large scale, and the obtained gold-magnetic composite particles have good dispersibility.
The invention is realized by the following technical scheme:
a preparation method of gold magnetic composite microspheres with monodispersity and superparamagnetism comprises the following steps:
(1) preparation of mesoporous Fe3O4
FeCl is added3·6H2Adding O and sodium acetate into 1, 2-propylene glycol, uniformly mixing to obtain a bright yellow mixed solution, heating to 90-110 ℃, and obtaining mesoporous Fe after the bright yellow mixed solution turns into ginger yellow3O4Precursor solution; mesoporous Fe3O4Carrying out solvothermal reaction on the precursor solution, separating out precipitate after reaction, washing and drying to obtain mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
Dissolving anhydrous sodium citrate in water, adding mesoporous Fe3O4Stirring the obtained mixed solution at room temperature to obtain the surface modified mesoporous Fe3O4A solution;
(3)Fe3O4preparation of Au composite microsphere
Modifying the surface of the mesoporous Fe3O4The solution was heated and then HAuCl was added4·4H2And (4) reacting the aqueous solution of O, separating out precipitate, washing and drying to obtain the gold-magnetic composite microsphere.
Preferably, in step (1), FeCl is added3·6H2The molar ratio of O to sodium acetate is (0.1-0.15): 1.
preferably, in the step (1), the solvothermal reaction temperature is 160-200 ℃, and the reaction time is 8-10 h.
Preferably, in the step (2), the anhydrous sodium citrate and the mesoporous Fe3O4The mass ratio of (0.05-0.5) g: (100-200) mg.
Preference is given toIn step (3), HAuCl4·4H2The mass ratio of O to anhydrous sodium citrate is (0.02-0.05) mg: (0.05-0.5) g.
Preferably, in the step (3), the temperature is heated to 100-110 ℃.
Preferably, in the step (3), the reaction time is 30-45 min.
Preferably, in step (3), the separation is magnetic separation and the drying is freeze-drying.
The gold-magnetic composite microsphere with monodispersity and superparamagnetism is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention firstly synthesizes superparamagnetism Fe by a solvothermal method3O4Then using reducing agent sodium citrate to react with Fe3O4Surface modification is carried out to make the particles have negative charges, and HAuCl is added4·4H2O, in this case, due to HAuCl4·4H2O with positive charge, HAuCl4·4H2O is adsorbed on Fe by electrostatic adsorption3O4On the surface of, and in Fe3O4The surface is reduced. Compared with the prior Fe3O4The invention is characterized in that sodium citrate is selected firstly, which not only can be used as a dispersing agent to Fe3O4Surface treatment is carried out, so that Fe is effectively avoided3O4(ii) agglomeration; secondly, it can also be used as a reducing agent directly in Fe3O4The surface is reduced in situ to obtain the monodisperse gold-magnetic composite microsphere, and the nano gold-magnetic composite material not only has Fe3O4The material has excellent performance in the field of biological catalysis due to the special electronic structure and synergistic effect between the two materials. The invention obtains monodisperse gold-magnetic composite particles in Fe3O4On the basis, the Au is compounded, so that the material still has stronger magnetism, and has good stability, dispersibility and biocompatibility. The invention obtainsThe surface of the gold magnetic composite particle is provided with a chemical bond with weaker citrate, and the gold magnetic composite particle can be connected with a required chemical group through coordination exchange to functionalize the surface of the particle and be used for developing more various composite materials to meet the actual requirements. The method has the advantages of simple operation, high yield, good repeatability and large-scale production.
Furthermore, the invention can control the content of the composite particle Au by regulating and controlling the content of the reducing agent, thereby realizing Fe3O4And the Au compounding proportion can be controlled and adjusted to meet the use requirements of the composite material in different application fields.
The gold-magnetic composite particles obtained by the invention have stronger magnetism, good stability, dispersibility and biocompatibility.
Drawings
FIG. 1 shows Fe prepared in example one3O4And (3) a transmission electron microscope image of the/Au composite microsphere.
FIG. 2 shows Fe prepared in example two3O4And (3) a transmission electron microscope image of the/Au composite microsphere.
FIG. 3 is Fe prepared in example III3O4And (3) a transmission electron microscope image of the/Au composite microsphere.
FIG. 4 is Fe prepared in example four3O4And (3) a transmission electron microscope image of the/Au composite microsphere.
FIG. 5 is Fe prepared in example V3O4And (3) a transmission electron microscope image of the/Au composite microsphere.
FIG. 6 is Fe prepared in example six3O4And (3) a transmission electron microscope image of the/Au composite microsphere.
FIG. 7 shows Fe prepared in example one3O4Ultraviolet-visible spectrum of the/Au composite microsphere.
FIG. 8 shows Fe prepared in example one3O4Magnetic hysteresis curves of the/Au composite microspheres.
FIG. 9 shows Fe prepared in example one3O4And (3) a transmission electron microscope image of the/Au composite microsphere.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of the gold-magnetic composite microsphere with monodispersity and superparamagnetism comprises the following steps:
(1) solvothermal method for preparing mesoporous Fe3O4
FeCl is added3·6H2Placing O and sodium acetate in a round-bottom flask, using a 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the O and the sodium acetate uniformly, then heating the uniformly stirred mixed solution to 90-110 ℃, transferring the mixture into a polytetrafluoroethylene reaction kettle, and reacting for 8-10 hours at 160-200 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4. Wherein FeCl3·6H2The molar ratio of O to sodium acetate is (0.1-0.15): 1.
(2) reducing agent to mesoporous Fe3O4Performing surface modification
Firstly, dissolving anhydrous sodium citrate in 100ml of ultrapure water, adding the mesoporous Fe in the step (1) after completely dissolving3O4Mechanically stirring the mixed solution at room temperature for 3-12h, and storing at 4 ℃ for later use. Anhydrous sodium citrate and mesoporous Fe3O4The mass ratio of (0.05-0.3) g: (100-200) mg.
(3)Fe3O4Preparation of Au composite microsphere
Firstly, the surface modified Fe in the step (2)3O4Heating the solution to 100-110 ℃, and then adding 2-5 ml HAuCl4·4H2And (3) reacting the O (1%) aqueous solution for 30-45 min to obtain a red solution, namely the gold-magnetic composite microspheres, performing magnetic separation, and washing off redundant colloidal gold by using ultrapure water until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
Example one
(1) Hydrothermal method for preparing mesoporous Fe3O4
Adding 5mmol of FeCl3·6H2O and 50mmol of sodium acetateTaking 40ml of 1, 2-propylene glycol solution as a solvent in a round-bottom flask, stirring and ultrasonically dissolving the 1, 2-propylene glycol solution uniformly, then heating the uniformly stirred mixed solution to 90 ℃, transferring the mixture into a polytetrafluoroethylene reaction kettle, and reacting for 8 hours at 160 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
0.05g of anhydrous sodium citrate is dissolved in 100ml of ultrapure water, and after complete dissolution, 100mg of the prepared mesoporous Fe in the step (1) is added3O4Mechanically stirring the mixed solution for 3h at room temperature, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 100 ℃ and then 0.02g of HAuCl was added4·4H2And O, reacting for 30min, enabling the solution to turn red to obtain the gold-magnetic composite microspheres, finally carrying out magnetic separation, and washing away excessive colloidal gold by using ultrapure water until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
Example two
(1) Hydrothermal method for preparing mesoporous Fe3O4
Adding 5mmol of FeCl3·6H2Placing O and 50mmol sodium acetate in a round-bottom flask, taking 40ml of 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the solution uniformly, then heating the uniformly stirred mixed solution to 95 ℃, transferring the heated mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 10 hours at 180 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
0.10g of anhydrous sodium citrate is dissolved in 100ml of ultrapure water, and after complete dissolution, 100mg of the prepared mesoporous Fe in the step (1) is added3O4Mechanically stirring the mixed solution at room temperature for 4h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 105 ℃ and 4ml HAuCl was added4·4H2Reacting with O (1%) water solution for 35min to obtain red gold-magnetic composite microsphere, magnetically separating, and washing with ultrapure water to remove excessive colloidal gold until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
EXAMPLE III
(1) Hydrothermal method for preparing mesoporous Fe3O4
Adding 5mmol of FeCl3·6H2Placing O and 30mmol sodium acetate in a round-bottom flask, taking 40ml 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the solution uniformly, then heating the uniformly stirred mixed solution to 100 ℃, transferring the mixture into a polytetrafluoroethylene reaction kettle, and reacting for 9 hours at 190 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
0.15g of anhydrous sodium citrate is dissolved in 100ml of ultrapure water, and after complete dissolution, 100mg of the prepared mesoporous Fe in the step (1) is added3O4Mechanically stirring the mixed solution at room temperature for 5h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 110 ℃ and 4ml HAuCl4·4H2Reacting with O (1%) water solution for 40min to obtain gold-magnetic composite microsphere, magnetically separating, and washing with ultrapure waterAnd (5) redundant colloidal gold is added until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
Example four
(1) Hydrothermal method for preparing mesoporous Fe3O4
Adding 5mmol of FeCl3·6H2Placing O and 35mmol sodium acetate in a round-bottom flask, taking 40ml 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the solution uniformly, then heating the uniformly stirred mixed solution to 105 ℃, transferring the mixture into a polytetrafluoroethylene reaction kettle, and reacting for 10 hours at the temperature of 200 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
Dissolving 0.20g of anhydrous sodium citrate in 100ml of ultrapure water, and adding 100mg of the prepared mesoporous Fe in the step (1) after complete dissolution3O4Mechanically stirring the mixed solution at room temperature for 6h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 105 ℃ and 3ml of HAuCl4·4H2Reacting with O (1%) water solution for 45min to obtain red gold-magnetic composite microsphere, magnetically separating, and washing with ultrapure water to remove excessive colloidal gold until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
EXAMPLE five
(1) Hydrothermal method for preparing mesoporous Fe3O4
Mixing 5mMFeCl3·6H2Placing O and 50mM sodium acetate in a round-bottom flask, taking 40ml of 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the 1, 2-propylene glycol solution uniformly, then heating the uniformly stirred mixed solution to 100 ℃, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and reacting 1 at 190 ℃And 0 h. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
Dissolving 0.4g of anhydrous sodium citrate in 100ml of ultrapure water, and adding 100mg of the prepared mesoporous Fe in the step (1) after complete dissolution3O4Mechanically stirring the mixed solution at room temperature for 7h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 105 ℃ and 4ml HAuCl4·4H2Reacting with O (1%) water solution for 40min to obtain red gold-magnetic composite microsphere, magnetically separating, and washing with ultrapure water to remove excessive colloidal gold until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
EXAMPLE six
(1) Hydrothermal method for preparing mesoporous Fe3O4
Mixing 5mMFeCl3·6H2Placing O and 40mM sodium acetate in a round-bottom flask, taking 40ml of 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the solution uniformly, then heating the uniformly stirred mixed solution to 110 ℃, transferring the mixture into a polytetrafluoroethylene reaction kettle, and reacting for 10 hours at 180 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
Dissolving 0.5g of anhydrous sodium citrate in 100ml of ultrapure water, and adding 100mg of the prepared mesoporous Fe in the step (1) after complete dissolution3O4Mechanically stirring the mixed solution at room temperature for 8h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 105 ℃ and 5ml HAuCl4·4H2Reacting with O (1%) water solution for 45min to obtain red gold-magnetic composite microsphere, magnetically separating, and washing with ultrapure water to remove excessive colloidal gold until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
EXAMPLE seven
(1) Hydrothermal method for preparing mesoporous Fe3O4
Adding 5mmol of FeCl3·6H2Placing O and 50mmol sodium acetate in a round-bottom flask, taking 40ml of 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the solution uniformly, then heating the uniformly stirred mixed solution to 110 ℃, transferring the mixture into a polytetrafluoroethylene reaction kettle, and reacting for 9 hours at 190 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
0.25g of anhydrous sodium citrate is dissolved in 100ml of ultrapure water, and after complete dissolution, 130mg of the mesoporous Fe prepared in the step (1) is added3O4Mechanically stirring the mixed solution at room temperature for 9h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 110 ℃ and 0.035g HAuCl4·4H2And O, reacting for 45min, enabling the solution to turn red to obtain the gold-magnetic composite microspheres, finally carrying out magnetic separation, and washing away excessive colloidal gold by using ultrapure water until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
Example eight
(1) Hydrothermal preparationMesoporous Fe3O4
Adding 5mmol of FeCl3·6H2Placing O and 45mmol sodium acetate in a round-bottom flask, taking 40ml of 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the solution uniformly, then heating the uniformly stirred mixed solution to 110 ℃, transferring the mixture into a polytetrafluoroethylene reaction kettle, and reacting for 8 hours at 190 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
Dissolving 0.35g of anhydrous sodium citrate in 100ml of ultrapure water, and adding 150mg of the prepared mesoporous Fe in the step (1) after complete dissolution3O4Mechanically stirring the mixed solution at room temperature for 10h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 110 ℃ and 0.04g HAuCl4·4H2And O, reacting for 45min, enabling the solution to turn red to obtain the gold-magnetic composite microspheres, finally carrying out magnetic separation, and washing away excessive colloidal gold by using ultrapure water until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
Example nine
(1) Hydrothermal method for preparing mesoporous Fe3O4
Adding 5mmol of FeCl3·6H2Placing O and 50mmol sodium acetate in a round-bottom flask, taking 40ml of 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the solution uniformly, then heating the uniformly stirred mixed solution to 110 ℃, transferring the mixture into a polytetrafluoroethylene reaction kettle, and reacting for 8 hours at the temperature of 200 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
0.45g of anhydrous sodium citrate is dissolved in 100ml of ultrapure water, and 180mg of the mesoporous Fe prepared in the step (1) is added after the anhydrous sodium citrate is completely dissolved3O4Mechanically stirring the mixed solution at room temperature for 11h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 105 ℃ and 0.035g HAuCl4·4H2And O, reacting for 40min, enabling the solution to turn red to obtain the gold-magnetic composite microspheres, finally carrying out magnetic separation, and washing away excessive colloidal gold by using ultrapure water until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
Example ten
(1) Hydrothermal method for preparing mesoporous Fe3O4
Adding 5mmol of FeCl3·6H2Placing O and 40mmol sodium acetate in a round-bottom flask, taking 40ml 1, 2-propylene glycol solution as a solvent, stirring and ultrasonically dissolving the solution uniformly, then heating the uniformly stirred mixed solution to 90 ℃, transferring the heated mixed solution into a polytetrafluoroethylene reaction kettle, and reacting for 10 hours at 170 ℃. After the reaction is finished, collecting black precipitate by using magnet magnetic separation, alternately cleaning the black precipitate for a plurality of times by using ultrapure water and absolute ethyl alcohol until the cleaned supernatant is clear, and finally freeze-drying to obtain powder, namely the mesoporous Fe3O4。
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
0.5g of anhydrous sodium citrate is dissolved in 100ml of ultrapure water, and after complete dissolution, 200mg of the mesoporous Fe prepared in the step (1) is added3O4Mechanically stirring the mixed solution at room temperature for 12h, and storing at 4 ℃ for later use.
(3)Fe3O4Preparation of Au composite microsphere
Modifying the sodium citrate modified Fe in the step (2)3O4The solution was heated to 105 ℃ and 0.05g of HAuCl4·4H2O, reactionAnd (4) after 45min, the solution turns red to obtain the gold-magnetic composite microspheres, and finally, carrying out magnetic separation, and washing off redundant colloidal gold by using ultrapure water until the supernatant is colorless and transparent. Freeze drying, collecting powder to obtain Fe3O4the/Au composite microsphere.
FIGS. 1-6 are Fe synthesized in examples one to six3O4Transmission electron micrograph of/Au composite microsphere, FIG. 9 is Fe synthesized in example one3O4The amplified transmission electron microscope image of the/Au composite microsphere shows pure black due to higher contrast of the Au simple substance under the TEM transmission electron microscope, and as shown in the figure, Au is loaded in mesoporous Fe3O4Surface, and no free Au is present. The composite particles have good dispersibility and no obvious agglomeration, and as can be seen from figures 1-6, the compounding amount of Au is obviously increased along with the increase of the use amount of sodium citrate. The final product of the invention is preserved in water with particularly good dispersibility, up to three months, and is also a homogeneous solution.
The existing method for preparing the gold-magnetic composite material by simultaneously adding the reducing agent and the Au precursor is unstable, can be stored for a long time, and can be layered (the precipitate below) and agglomerated.
FIG. 7 shows Fe synthesized in example one3O4Ultraviolet-visible spectrum of the/Au composite microsphere. With pure Fe3O4In contrast, Fe3O4the/Au composite material has a characteristic absorption peak 534nm of the simple substance Au, and well proves the successful combination of the simple substance Au.
FIG. 8 shows Fe synthesized in example one3O4Magnetic hysteresis curves of the/Au composite microspheres. The two curves are both in an S shape, which accords with superparamagnetism, and Fe is not influenced after the Au simple substance is compounded3O4Structure and magnetic properties of (a).
Claims (4)
1. A preparation method of gold-magnetic composite microspheres with monodispersity and superparamagnetism is characterized by comprising the following steps:
(1) preparation of mesoporous Fe3O4
FeCl is added3·6H2Adding O and sodium acetate into 1, 2-propylene glycol, and mixing to obtain bright yellowHeating the mixed solution to 90-110 ℃, and obtaining mesoporous Fe after the bright yellow mixed solution turns into ginger yellow3O4Precursor solution; mesoporous Fe3O4Carrying out solvothermal reaction on the precursor solution, separating out precipitate after reaction, washing and drying to obtain mesoporous Fe3O4；
(2) Reducing agent to mesoporous Fe3O4Performing surface modification
Dissolving anhydrous sodium citrate in water, adding mesoporous Fe3O4Stirring the obtained mixed solution at room temperature to obtain the surface modified mesoporous Fe3O4A solution;
（3）Fe3O4preparation of Au composite microsphere
Modifying the surface of the mesoporous Fe3O4The solution was heated and then HAuCl was added4·4H2O water solution, separating out precipitate after reaction, washing and drying to obtain the gold magnetic composite microsphere with monodispersity and superparamagnetism;
in step (1), wherein FeCl3·6H2The molar ratio of O to sodium acetate is (0.1-0.15): 1;
in the step (2), anhydrous sodium citrate and mesoporous Fe3O4The mass ratio of (0.05-0.5) g: (100-200) mg;
in step (3), HAuCl4·4H2The mass ratio of O to anhydrous sodium citrate is (0.02-0.05) mg: (0.05-0.5) g;
in the step (3), heating to 100-110 ℃.
2. The preparation method of gold-magnetic composite microspheres with monodispersity and superparamagnetism according to claim 1, wherein in the step (1), the solvothermal reaction temperature is 160-200 ℃, and the reaction time is 8-10 h.
3. The method for preparing gold-magnetic composite microspheres with monodispersity and superparamagnetism according to claim 1, wherein in the step (3), the reaction time is 30-45 min.
4. The method for preparing gold-magnetic composite microspheres with monodispersity and superparamagnetism as claimed in claim 1, wherein in the step (3), the separation is magnetic separation, and the drying is freeze-drying.
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| CN109844514A (en) * | 2018-06-21 | 2019-06-04 | 云南大学 | The preparation method and applications of the electrochemical sensor of non-coding RNA |
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| CN106040307A (en) * | 2016-06-06 | 2016-10-26 | 北京科技大学 | Preparation method for synthesizing Fe3O4(PAA)@C-Au core-shell-structured microspheres with one-step hydrothermal method |
| CN109844514A (en) * | 2018-06-21 | 2019-06-04 | 云南大学 | The preparation method and applications of the electrochemical sensor of non-coding RNA |
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