CN115255360A - High-performance FePt @ Fe shell-core structure magnetic nanocrystal and preparation method thereof - Google Patents
High-performance FePt @ Fe shell-core structure magnetic nanocrystal and preparation method thereof Download PDFInfo
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Images
Classifications
-
- 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
- B22F1/17—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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
Abstract
The invention discloses a high-performance FePt @ Fe shell-core structure magnetic nanocrystal and a preparation method thereof. The metal alloy-metal particle shell-core structure nanocrystal comprises a core region and a shell region; the material constituting the core region is a metal alloy, and the material constituting the shell region is a metal atom. The metal alloy-metal atom shell-core structure nanocrystalline prepared by the invention has small size and wide magnetic performance regulation and control, and can be used for structural elements of magnetic devices such as magnetic recording, magnetic storage and the like. The metal alloy-metal shell-core structure nanocrystalline prepared by the invention has wide regulation and control of magnetic performance, can regulate saturation magnetization intensity to be high or low, and can be used as a contrast agent or a magnetic probe for MRI (magnetic resonance imaging), ultra-low field imaging and the like. The invention provides a simple, high-efficiency and low-cost halogen one-pot synthesis method, which can prepare the metal alloy-metal atomic shell-core structure nanocrystalline which is synthesized in a large scale, has good monodispersity and has super-controllable magnetic property.
Description
Technical Field
The invention relates to a high-performance FePt @ Fe shell core structure magnetic nanocrystal and a preparation method thereof, belonging to the field of nanomaterial science.
Background
Exchange-coupled nanocomposites with shell/core phases hold great promise as next-generation magnetic memory materials. Because magnetic coupling exchange interaction exists between the core and the shell, the magnetic coupling interaction can be regulated and controlled by regulating and controlling the size, crystallinity and interface, and further basic magnetic properties such as saturation magnetization, remanence property, blocking temperature and the like of the material are optimized, so that the application in the fields of medicine, aviation, biology, materials and the like is realized.
However, at present, the preparation of the magnetic material with the core-shell structure is mostly carried out by adopting a seed-mediated growth method, the operation of the methods is complex, a high-temperature calcination process is required, not only is time consumed and a reagent is consumed, but also the prepared core-shell material has poor monodispersity, and the morphology and the property of particles are difficult to regulate and control. Further limiting the magnetic performance and application research of the shell-core particles. Therefore, a simple and efficient method is designed, and the preparation of the shell-core material with good monodispersity and controllable crystal form has important scientific significance and value.
Disclosure of Invention
The invention aims to provide a metal alloy-metal atom shell-core structure nanocrystal, which is synthesized by adopting a halogen-mediated one-pot method, can adjust the shell-core structure from the aspect of size, and can also adjust the crystal form of the shell-core dual-magnetic nanocrystal; the method has the characteristics of simplicity, high efficiency and low cost, and can be used for preparing the metal alloy-metal particle shell-core structure nanocrystalline which is synthesized in large scale, has good monodispersity and has super-controllable magnetic property.
The metal alloy-metal particle shell-core structure nanocrystal provided by the invention comprises a core area and a shell area;
the material constituting the nuclear region is a metal alloy;
the material constituting the shell region is a metal atom.
Preferably, the metal alloy is a face-centered tetragonal platinized iron alloy (chemical formula is FePt), wherein the atomic number ratio of platinum to iron is 1:1;
the metal atoms are iron atoms, and can be expanded to other metal atoms according to the needs.
The metal alloy-metal particle shell-core structure nanocrystal provided by the invention is preferably FePt @ Fe shell-core nanocrystal;
wherein the diameter of the nuclear region is 3-10 nm;
the grain diameter of the shell-core structure nanocrystal is 3-11 nm.
The invention also provides a preparation method of the core-shell structure nanocrystal, which comprises the following steps:
and mixing the precursor of the metal alloy and the precursor of the metal atom in the same closed reaction vessel under the protection of inert atmosphere, adding an organic phase and a halogen source, and reacting by adopting an oil phase high-temperature thermal decomposition method to obtain the metal alloy.
In the above preparation method, the precursor of the metal alloy is a mixture of platinum acetylacetonate and iron acetylacetonate;
the precursor of the metal atom is ferric acetylacetonate;
the inert atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
In the above preparation method, the organic phase is a mixture of a stabilizer, a reducing agent and a solvent;
the stabilizer is oleylamine and oleic acid;
the reducing agent is 1,2-hexadecanediol;
the solvent is at least one of octadecene, hexadecene, dibenzyl ether and squalane;
the halogen source is ammonium chloride or sodium chloride.
In the preparation method, the reaction time of the oil phase high-temperature thermal decomposition method is 30 min-2 h, and the temperature is 180-300 ℃.
In the above preparation method, the molar ratio of the precursor of the metal alloy, the reducing agent, the precursor of the metal atom, the halogen source, the oleylamine, the oleic acid, and the solvent is: 1:1 to 20:1:1 to 9:2 to 50:2 to 50:30 to 320, preferably 1:3:6: 6-10: 6-10: 3:62.5, 1:3:6:6:6:3:62.5 or 1:3:6:6:6:3:62.5.
after the oil phase is subjected to high-temperature thermal decomposition reaction, the method also comprises the following steps: centrifugally washing, collecting the solid product, then resuspending the solid product in a good solvent to obtain a solution of the magnetic nanocrystal with the core-shell structure, and refrigerating and storing the solution;
the conditions for the centrifugal washing may be: adding precipitant, rotating speed 3000-8000 r/min, centrifuging time 5-20 min; specifically, ethanol solvent is added, the mixture is centrifuged at 5000r/min for 10min, and the centrifugation is repeated for 5 times.
The core-shell structure nanocrystal provided by the invention can be used for at least one of the following 1) to 5):
1) Preparing a catalytic material;
2) Preparing a magnetic storage material;
3) Magnetic imaging detection of cells;
4) Preparing an ultra-low field probe;
5) Preparing the contrast agent for magnetic resonance imaging.
The invention has the following advantages:
1. the preparation method can obtain the core-shell structure magnetic nanomaterial without multi-pot synthesis, avoids the defects of complex steps of synthesizing the core-shell structure by a seed method, waste of experiment consumable reagents and waste of time, and is simple, efficient, low in cost and time-saving.
2. The magnetic nanocrystal with the core-shell structure prepared by the invention is in a nanometer level, and has good monodispersity and uniform size.
3. The crystal forms of the shell and the core of the magnetic nanocrystalline material with the core-shell structure are controllable, and the crystal form of the whole nanocrystalline material can be controlled by adjusting the proportion of the halogen source participating in the reaction.
4. The magnetic property of the magnetic nanocrystal with the core-shell structure prepared by the invention is controllable, and the magnetic property of the whole nanomaterial is adjusted by adjusting the nanocrystal.
5. The material can be purchased, the method is novel, the process is simple, the equipment is common, the controllability is good, the function is strong, and a large amount of double-magnetic functional nano magnetic materials with shell-core structures can be prepared at one time.
6. The metal alloy-metal atom shell-core structure nanocrystalline prepared by the invention has small size and wide magnetic performance regulation and control, and can be used for structural elements of magnetic devices such as magnetic recording, magnetic storage and the like.
7. The metal alloy-metal shell-core structure nanocrystalline prepared by the invention has wide regulation and control of magnetic performance and adjustable high and low saturation magnetization intensity, and can be used as a contrast agent or a magnetic probe for MRI (magnetic resonance imaging), ultra-low field imaging and the like.
In conclusion, the invention provides a simple, high-efficiency and low-cost halogen one-pot synthesis method, and the metal alloy-metal atomic shell-core structure nanocrystalline which is synthesized in large scale, has good monodispersity and has super-controllable magnetic property can be prepared.
Drawings
FIG. 1 is a schematic diagram of a device and nanocrystals of FePt @ Fe shell core magnetic nanocrystals prepared in example 1 of the present invention.
FIG. 2 is a high-resolution transmission electron microscope (HTEM) image and an element scan image of FePt @ Fe shell core magnetic nanocrystal prepared in example 1 of the present invention; wherein, FIG. 2a is a high-resolution transmission electron microscope (HTEM) image of FePt @ Fe shell-core magnetic nanocrystal, and FIG. 2b, FIG. 2c and FIG. 2d are the combined images of a platinum element scan, an iron element scan and a platinum-iron element scan, respectively.
FIG. 3 is a Transmission Electron Microscope (TEM) image of FePt nanoparticles prepared in example 2 of the present invention.
FIG. 4 is a Transmission Electron Microscope (TEM) image of FePt @ Fe shell-core structure nanocrystals prepared in example 3 of the present invention.
FIG. 5 is a graph showing the results of X-ray powder diffraction (XRD) tests of FePt @ Fe shell-core magnetic nanocrystals prepared in example 1 of the present invention and FePt nanoparticles prepared in example 2.
FIG. 6 is a magnetic property (H-M) curve, 5K, of FePt @ Fe shell-core magnetic nanocrystals prepared in example 1 and FePt nanoparticles prepared in example 2 of the present invention.
FIG. 7 is a curve of FC-ZFC measured by FePt @ Fe shell core magnetic nanocrystals prepared in example 1 of the present invention.
FIG. 8 is a plot of the FC-ZFC curves measured for FePt nanoparticles prepared in example 2 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of tetragonal form-oriented FePt @ Fe shell-core structure nanocrystal
The preparation was carried out in the apparatus shown in FIG. 1, in the following manner:
0.5mmol of platinum acetylacetonate, 1.5mmol of 1, 2-hexadecanediol and 20mL of 1-octadecene are added into a 150mL three-necked flask, magnetic stirring is carried out at 1600rpm/min, the mixture is uniformly mixed, vacuum is carried out at 40 ℃ for 30min, nitrogen is introduced, 1.6mL of oleic acid, 1.7mL of oleylamine, 1.5mmol of ammonium chloride and 3mmol of ferric acetylacetonate (platinum acetylacetonate: 1,2-hexadecanediol: ferric acetylacetonate: oleic acid: oleylamine: ammonium chloride: 1-octadecene ratio is 1. Removing a heat source, cooling to room temperature, adding a proper amount of ethanol, performing 6000r/min centrifugal separation for 10min, taking a precipitate, adding a proper amount of cyclohexane to dissolve a product, performing 6000r/min centrifugal separation for 10min again, taking an upper layer liquid, repeating the ethanol precipitation/cyclohexane dispersion process for 3 times, and finally directly using the prepared magnetic nanoparticles in the next experiment or dispersing the magnetic nanoparticles in a sample bottle and placing the sample bottle in a refrigerator at 4 ℃.
FIG. 2 shows a high-resolution transmission electron microscope (HTEM) picture of the FePt @ Fe shell-core structure nanocrystal prepared in example 1 of the present invention. XRD characterization of the FePt @ Fe shell-core structured nanocrystals prepared by the present invention, example 1, is shown in FIG. 5. The magnetic properties of the FePt @ Fe shell-core structure nanocrystal prepared from the present invention in example 1 are shown in FIGS. 6 and 7.
As can be seen from FIG. 2, the nanocrystals prepared by the present invention have a shell-core structure, the whole nanocrystals are pea-shaped and uniform in size, the average size of the core is about 7.4nm, and the average thickness of the shell is about 0.46nm. FIG. 5 shows that the diffraction peaks measured by the FePt @ Fe shell-core structure nanocrystal prepared by the invention respectively correspond to the peak positions of the face-centered tetragonal FePt nanoparticles and the pure Fe particles.
Example 2: preparation of FePt nanocrystals was compared to example 1
0.5mmol of platinum acetylacetonate, 1.5mmol of 1, 2-hexadecanediol and 20mL of 1-octadecene are added into a 150mL three-necked flask, magnetic stirring is carried out at 1600rpm/min, the mixture is uniformly mixed, vacuum pumping is carried out at 40 ℃ for 30min, nitrogen is introduced, 1.6mL of oleic acid, 1.7mL of oleylamine and 3mmol of iron acetylacetonate (platinum acetylacetonate: 1,2-hexadecanediol: iron acetylacetonate: oleic acid: oleylamine: 1-octadecene ratio is 1. Removing a heat source, cooling to room temperature, adding a proper amount of ethanol, carrying out 6000r/min centrifugal separation for 10min, taking a precipitate, adding a proper amount of cyclohexane, dissolving a product, carrying out 6000r/min centrifugal separation for 10min again, taking an upper layer liquid, repeating the ethanol precipitation/cyclohexane dispersion process for 3 times, and finally directly using the prepared magnetic nanoparticles in the next experiment or dispersing the magnetic nanoparticles in a sample bottle and placing the sample bottle in a refrigerator at 4 ℃.
A Transmission Electron Microscope (TEM) picture of the FePt nanocrystal prepared from this example 2 is shown in fig. 3. XRD characterization of FePt nanoparticles prepared from example 2 is shown in fig. 5. The magnetic properties of the FePt nanoparticles prepared from example 2 are characterized as shown in fig. 6 and 8.
As can be seen from fig. 3, the prepared nanoparticles have an oval shape and a uniform size, and the average size is about 5nm. As can be seen from fig. 5, the diffraction peak measured by the prepared FePt nanoparticle corresponds to the peak position of the cubic FCC structure of the pure FePt nanoparticle, which indicates that the FCT face-centered tetragonal crystal peak of the FePt nanoparticle appears after the halogen source is added in the preparation process, and the FCT face-centered tetragonal crystal peak does not appear without the halogen source. Comparing fig. 6, 7, and 8, it can be seen that the fept @ fe shell-core structure nanocrystal prepared in example 1 has higher saturation magnetization and blocking temperature due to the magnetic coupling exchange interaction between the core and the shell.
Example 3: preparation of FePt @ Fe shell core structure nanocrystals with different sizes
0.5mmol of platinum acetylacetonate, 1.5mmol of 1, 2-hexadecanediol and 20mL of 1-octadecene are added into a 150mL three-necked flask, magnetic stirring is carried out at 1600rpm/min, uniform mixing is carried out, vacuum is carried out at 40 ℃ for 30min, nitrogen is introduced, a 1mL of oleic acid, 1mL of oleylamine, 1.5mmol of ammonium chloride and 3mmol of iron acetylacetonate (platinum acetylacetonate: 1,2-hexadecanediol: iron acetylacetonate: oleic acid: oleylamine: ammonium chloride: 1-octadecene ratio is 1. Removing a heat source, cooling to room temperature, adding a proper amount of ethanol, carrying out 6000r/min centrifugal separation for 10min, taking a precipitate, adding a proper amount of cyclohexane, dissolving a product, carrying out 6000r/min centrifugal separation for 10min again, taking an upper layer liquid, repeating the ethanol precipitation/cyclohexane dispersion process for 3 times, and finally directly using the prepared magnetic nanoparticles in the next experiment or dispersing the magnetic nanoparticles in a sample bottle and placing the sample bottle in a refrigerator at 4 ℃.
A Transmission Electron Microscope (TEM) picture of the FePt @ Fe shell-core structure nanocrystal prepared in example 3 is shown in FIG. 4. As can be seen from fig. 4, the prepared nanoparticles have an oval shape and a uniform size, the average size of the core is about 6nm, and the average thickness of the shell is about 0.3nm. It can be seen by comparing example 1 and example 3 that when the surface ligand is at a low concentration, the size of the product nanoparticles becomes smaller. It was demonstrated that the size of the nanoparticles can be adjusted by surface ligands.
Claims (10)
1. A metal alloy-metal particle shell-core structure nanocrystal comprises a core region and a shell region; the method is characterized in that:
the material constituting the nuclear region is a metal alloy;
the material constituting the shell region is a metal atom.
2. The core-shell nanocrystal of claim 1, wherein: the metal alloy is a face-centered tetragonal platinized iron alloy;
the metal atom is an iron atom.
3. The core-shell nanocrystal of claim 2, wherein: the core-shell structure nanocrystal is FePt @ Fe core-shell structure nanocrystal.
4. The shell-core structured nanocrystal of any one of claims 1 to 3, wherein: the diameter of the nuclear region is 3-10 nm;
the grain diameter of the shell-core structure nanocrystal is 3-11 nm.
5. A method for preparing the core-shell structured nanocrystal, according to any one of claims 1 to 4, comprising the steps of:
and mixing the precursor of the metal alloy and the precursor of the metal atom in the same closed reaction vessel under the protection of inert atmosphere, adding an organic phase and a halogen source, and reacting by adopting an oil phase high-temperature thermal decomposition method to obtain the metal alloy.
6. The production method according to claim 5, characterized in that: the precursor of the metal alloy is a mixture of platinum acetylacetonate and iron acetylacetonate;
the precursor of the metal atom is ferric acetylacetonate;
the inert atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
7. The production method according to claim 5 or 6, characterized in that: the organic phase is a mixture of a stabilizer, a reducing agent and a solvent;
the stabilizer is oleylamine and oleic acid;
the reducing agent is 1,2-hexadecanediol;
the solvent is at least one of octadecene, hexadecene, dibenzyl ether and squalane;
the halogen source is ammonium chloride.
8. The production method according to any one of claims 5 to 7, characterized in that: the reaction time of the oil phase high-temperature thermal decomposition method is 30 min-2 h, and the temperature is 180-300 ℃.
9. The production method according to any one of claims 7 or 8, characterized in that: the molar ratio of the precursor of the metal alloy, the reducing agent, the precursor of the metal atom, the halogen source, the oleylamine, the oleic acid and the solvent is: 1:1 to 20:1:1 to 9:2 to 50:30 to 320.
10. Use of the core-shell nanocrystals according to any one of claims 1 to 4 in at least one of the following 1) to 5):
1) Preparing a catalytic material;
2) Preparing a magnetic storage material;
3) Magnetic imaging detection of cells;
4) Preparing an ultra-low field probe;
5) Preparing the contrast agent for magnetic resonance imaging.
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